WO2011013720A1 - Unsaturated urethane oligomer, curable resin composition, transparent laminate, and process for producing same - Google Patents

Unsaturated urethane oligomer, curable resin composition, transparent laminate, and process for producing same Download PDF

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Publication number
WO2011013720A1
WO2011013720A1 PCT/JP2010/062731 JP2010062731W WO2011013720A1 WO 2011013720 A1 WO2011013720 A1 WO 2011013720A1 JP 2010062731 W JP2010062731 W JP 2010062731W WO 2011013720 A1 WO2011013720 A1 WO 2011013720A1
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Prior art keywords
resin composition
curable resin
polyol
mass
transparent
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PCT/JP2010/062731
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French (fr)
Japanese (ja)
Inventor
宜伸 門脇
聡 新山
直子 青木
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旭硝子株式会社
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Application filed by 旭硝子株式会社 filed Critical 旭硝子株式会社
Priority to CN201080034486.0A priority Critical patent/CN102471449B/en
Priority to JP2011524819A priority patent/JP5737180B2/en
Publication of WO2011013720A1 publication Critical patent/WO2011013720A1/en

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/67—Unsaturated compounds having active hydrogen
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    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
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    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/10009—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets
    • B32B17/10036—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the number, the constitution or treatment of glass sheets comprising two outer glass sheets
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    • B32B17/10899—Making laminated safety glass or glazing; Apparatus therefor by introducing interlayers of synthetic resin
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F290/00—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups
    • C08F290/02—Macromolecular compounds obtained by polymerising monomers on to polymers modified by introduction of aliphatic unsaturated end or side groups on to polymers modified by introduction of unsaturated end groups
    • C08F290/06—Polymers provided for in subclass C08G
    • C08F290/067—Polyurethanes; Polyureas
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
    • C08G18/3878—Low-molecular-weight compounds having heteroatoms other than oxygen having phosphorus
    • C—CHEMISTRY; METALLURGY
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    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C08G18/6461—Macromolecular compounds not provided for by groups C08G18/42 - C08G18/63 having phosphorus
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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    • C—CHEMISTRY; METALLURGY
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Definitions

  • the present invention relates to a flame retardant unsaturated urethane oligomer suitable for a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates, and a curing containing the unsaturated urethane oligomer.
  • the present invention relates to a curable resin composition, a transparent laminate having a cured resin layer composed of a cured product of the curable resin composition, and a method for producing a transparent laminate using the curable resin composition.
  • a laminated glass in which a pair of glass plates are integrated via an adhesive resin layer is known.
  • the laminated glass is used as a windshield for automobiles because broken glass fragments adhere to the film-like adhesive resin layer and do not scatter.
  • the laminated glass is used as a window glass for buildings (safety glass, crime prevention glass, fire prevention safety glass, etc.) because it is difficult to penetrate and has excellent strength. Therefore, when used as a window glass, the adhesive resin layer may be required to have good flame retardance in addition to excellent transparency.
  • Fireproof safety glass is a glass that functions as a fire door during a fire and functions as a safety glass during normal times.
  • the resin material used for the adhesive resin layer of laminated glass gradually decomposes into low molecular weight substances when the decomposition temperature is reached. If the temperature that decomposes into volatile substances is higher than the ignition temperature of the volatile substances that are generated, it will ignite and ignite. Therefore, the resin material of the adhesive resin layer for fire safety safety glass includes a resin material that suppresses the oxidation reaction of the decomposition product, a resin material that does not volatilize even if the decomposition product is generated, and is crosslinked simultaneously with thermal decomposition. It is necessary to use a resin material that carbonizes by causing a reaction or a cyclization reaction, that is, a resin material having high flame retardancy.
  • the following are proposed as laminated glass using a resin material having high flame retardancy as the resin material of the adhesive resin layer.
  • Fire safety glass using a fluorine-containing copolymer as a resin material for the adhesive resin layer (Patent Document 1).
  • (2) Laminated glass obtained by adding a phosphorus-based flame retardant to the resin material of the adhesive resin layer (Patent Document 2).
  • the flame retardance is improved, but the adhesion between the glass plate and the adhesive resin layer is insufficient. Therefore, a haze value becomes high and it is difficult to use it as a window glass.
  • the laminated glass of (2) since the phosphorus-based flame retardant is not easily mixed with the resin material of the adhesive resin layer, the transparency is impaired or the flame retardancy is not uniform.
  • the amount of phosphorus-based flame retardant added is large, the mechanical properties such as the strength of the adhesive resin layer are impaired, or the added flame retardant migrates inside the adhesive resin layer over time. Problems occur.
  • Patent Document 3 a urethane prepolymer composition using a phosphorus-containing flame retardant polyol as a raw material is disclosed.
  • this urethane prepolymer composition is used for the adhesive resin layer of laminated glass, there is a concern about durability.
  • the following method is known as a manufacturing method of a laminated glass.
  • (I) A method of producing a laminated glass by sandwiching an adhesive resin film between a pair of transparent substrates and thermocompression bonding the laminate.
  • (Ii) A method of manufacturing a laminated glass by injecting a liquid curable resin between a pair of transparent substrates whose periphery is sealed, and then curing the curable resin (Patent Document 4).
  • the method (ii) has a wider variety of curable resins than the method (i), and it is easy to obtain a cured product having various physical properties according to the purpose, and an easily curable resin (especially a photocurable resin). ) Can be used to simplify the manufacturing process.
  • the method (ii) has a drawback that bubbles tend to remain in the resin when the curable resin is injected.
  • a vacuum lamination method As a method for preventing the generation of bubbles, a vacuum lamination method is known.
  • the following method is known as a method for producing laminated glass by the reduced pressure lamination method.
  • a layer of the photocurable resin composition is formed on one transparent substrate, and another transparent substrate is stacked on the layer of the photocurable resin composition under reduced pressure to form a pair of transparent
  • a method for producing a laminated glass, in which a photocurable resin composition is sealed between substrates and then photocured under atmospheric pressure Patent Document 5).
  • a photocurable resin composition containing an unsaturated urethane oligomer As a photocurable resin composition, a photocurable resin composition containing an unsaturated urethane oligomer has been proposed (Patent Document 5). Moreover, the photocurable resin composition containing an unsaturated urethane oligomer is known also as a photocurable resin composition suitable for the method of (iii) (patent document 6). In the photocurable resin composition containing an unsaturated urethane oligomer, the characteristics of the cured product can be adjusted by using an unsaturated urethane oligomer and various monomers in combination. However, the conventional photocurable resin composition cannot obtain a cured product having good flame retardancy.
  • the present invention provides an unsaturated urethane oligomer and a curable resin composition capable of obtaining a cured product having excellent transparency and flame retardancy. Moreover, the curable resin composition used for the method of manufacturing a transparent laminated body is provided. Furthermore, the transparent laminated body which is excellent in transparency and excellent in a flame retardance, and its manufacturing method are provided.
  • the present invention is the following [1] to [15].
  • Polyol component (A1) A polyol component containing the following polyol (a1).
  • Polyol (a1) A polyol having 2 to 3 hydroxyl groups per molecule, a hydroxyl value of 35 to 150 mgKOH / g, and having a phosphorus atom in the molecule.
  • Curable functional group CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  • a curable resin composition comprising the unsaturated urethane oligomer (A) of [1] or [2].
  • the curable resin composition according to [3] which is a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates.
  • a transparent laminate having a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates, wherein the cured resin is a curable resin composition of [4] to [8] A transparent laminate that is a cured product of the above. [10] The transparent laminate according to [9], wherein at least one of the pair of transparent substrates is a glass plate.
  • a pair of transparent substrates and the pair of transparent substrates are formed between the pair of transparent substrates in a reduced-pressure atmosphere by forming a sealed space in which the curable resin composition of [4] to [8] is accommodated.
  • a first step of producing a laminated precursor having the curable resin composition sealed in between, and the laminated precursor is placed in an atmosphere having a pressure higher than the reduced-pressure atmosphere, and the curing is performed in the atmosphere.
  • the manufacturing method of a transparent laminated body which has a 2nd process of hardening an adhesive resin composition.
  • the method according to [11] wherein the reduced-pressure atmosphere is a pressure atmosphere of 100 Pa or less, and the atmosphere having a higher pressure than the reduced-pressure atmosphere is an atmospheric pressure atmosphere.
  • the curable resin composition is a photocurable resin composition, and in the second step, the laminated precursor is irradiated with light to cure the curable resin composition.
  • Manufacturing method is a photocurable resin composition, and in the second step, the laminated precursor is irradi
  • a curable resin composition comprising the unsaturated urethane oligomer (A) of [14].
  • a cured product having excellent transparency and flame retardancy can be obtained.
  • a curable resin composition of the present invention a cured product having excellent transparency and flame retardancy can be obtained.
  • the transparent laminate of the present invention is excellent in transparency and flame retardancy. According to the method for producing a transparent laminate of the present invention, a transparent laminate having excellent transparency and excellent flame retardancy can be produced.
  • the curable functional group represented by CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group) is an acryloyloxy group (where R is a hydrogen atom). Or a methacryloyloxy group (when R is a methyl group), and the group represented by the formula is also referred to as a (meth) acryloyloxy group.
  • (meth) acrylate is used as a general term for “acrylate” and “methacrylate”.
  • the unsaturated urethane oligomer (A) of the present invention is a urethane (meth) acrylate oligomer having an average of 2 to 4 curable functional groups described below per molecule and a phosphorus content of 1 to 6% by mass.
  • Curable functional group CH 2 ⁇ C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  • the unsaturated urethane oligomer (A) is suitable as one component of a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates. It is. Since the unsaturated urethane oligomer (A) has a phosphorus atom in the molecule, the cured product has flame retardancy.
  • the average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is 2 to 4, and preferably 2 to 3. If the average number of curable functional groups is 2 or more, a crosslinked structure can be introduced into a part of the cured resin layer, heat resistance is increased, and the cured resin layer is less likely to flow and deform when exposed to high temperatures. If the average number of curable functional groups is 4 or less, the crosslink density will not be too high, the flexibility of the cured resin layer will be good, and the impact resistance will be good.
  • the average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is the number of hydroxyl groups of the polyol component (A1), the number of isocyanate groups of the polyisocyanate compound (A2), and the curability of the unsaturated hydroxy compound (A3). It is adjusted by the number of functional groups and the number of hydroxyl groups. Diisocyanate having 2 isocyanate groups is preferable as the polyisocyanate compound (A2), and unsaturated monool having 1 curable functional group is preferable as the unsaturated hydroxy compound (A3).
  • the average number of curable functional groups per molecule of the obtained unsaturated urethane oligomer (A) is usually substantially the same as the average number of hydroxyl groups per molecule of the polyol component (A1).
  • an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 can be obtained.
  • diol and triol as the polyol component (A1), an unsaturated urethane oligomer (A) having an average curable functional group number between 2 and 3 is obtained, and only triol is obtained as the polyol component (A1).
  • an unsaturated urethane oligomer (A) having an average number of curable functional groups of 3 is obtained.
  • a plurality of curable functional groups present in one molecule may be the same or different. However, usually, when having a plurality of curable functional groups in one molecule, it is preferable that they have the same curable functional group.
  • the curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group.
  • the curable functional group in the unsaturated urethane oligomer (A) tends to be less reactive as the unsaturated urethane oligomer (A) has a higher molecular weight, and when used in combination with a relatively low molecular weight compound, both cure.
  • the curable functional group in the unsaturated urethane oligomer (A) is high. Therefore, the curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group having a higher reactivity than the methacryloyloxy group.
  • the phosphorus content in the unsaturated urethane oligomer (A) (100% by mass) is 1 to 7% by mass, preferably 1 to 4% by mass.
  • the phosphorus content is 1% by mass or more, a sufficient flame retardant effect can be obtained.
  • the phosphorus content is 7% by mass or less, there is no generation of heterogeneous oligomers due to high molecular weight (gelation) of oligomers or lowering of compatibility during the production of unsaturated urethane oligomer (A), and curing. Since the cured
  • the unsaturated urethane oligomer (A) is a reaction product of the polyol component (A1), the polyisocyanate compound (A2), and the unsaturated hydroxy compound (A3).
  • Examples of a method for obtaining the reaction product include the following: Examples thereof include the methods (1) to (3). (1) A method in which a polyol component (A1), a polyisocyanate compound (A2), and an unsaturated hydroxy compound (A3) are simultaneously reacted. (2) After reacting the polyisocyanate compound (A2) and the unsaturated hydroxy compound (A3) in a stoichiometrically excessive condition with an isocyanate group, the resulting reaction product is further reacted with a polyol component (A1). How to make.
  • the method (1) is easy, variations in the molecular weight and viscosity of the unsaturated urethane oligomer (A) are easily observed, which is not industrially preferable.
  • the method (2) when the number of hydroxyl groups in the polyol component (A1) is 3 or more, an ultrahigh molecular weight product (gel component) is hardly generated.
  • the method (3) is industrially preferable because a qualitative unsaturated urethane oligomer (A) can be obtained constantly.
  • Examples of the method (3) include a method having the following step (3-1) and step (3-2).
  • (3-1) If necessary, the polyol component (A1) and the polyisocyanate compound (A2) are reacted in the presence of a stoichiometric excess of isocyanate groups in the presence of a urethanization catalyst to obtain an isocyanate group-terminated urethane prepolymer. Obtaining.
  • (3-2) A step of reacting the unsaturated hydroxy compound (A3) with an isocyanate group at the terminal of the urethane prepolymer in the presence of a polymerization inhibitor as necessary.
  • Step (3-1) Examples of urethanization catalysts include cobalt naphthenate, zinc naphthenate, zinc 2-ethylhexanoate, dibutyltin dilaurate, tin 2-ethylhexanoate, triethylamine, 1,4-diabicyclo [2.2.2] octane, and the like. It is done.
  • the ratio of the polyol component (A1) and the polyisocyanate compound (A2) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1.2: 1 to 3: 1, and is 1.2: 1 to 2: 1. Is more preferred.
  • the reaction temperature is preferably a temperature in a normal urethanization reaction, that is, 30 to 90 ° C.
  • the polymerization inhibitor examples include hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-hydroquinone, o-nitrotoluene and the like.
  • the amount of the polymerization inhibitor is preferably 50 to 5,000 ppm based on the unsaturated hydroxy compound (A3).
  • the ratio of the urethane prepolymer and the unsaturated hydroxy compound (A3) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1: 1 to 1: 1.5.
  • the reaction temperature is preferably 30 to 90 ° C.
  • the polyol component (A1) is a polyol component containing a polyol (a1) having a phosphorus atom in the molecule as an essential component, preferably further containing a polyol (a2), and if necessary, another polyol (a3). May be included.
  • the phosphorus content in the polyol component (A1) (100% by mass) is more than 1% by mass, preferably 10% by mass or less, and more preferably 1.1 to 8.5% by mass.
  • the polyol component (A1) having a phosphorus content exceeding 1% by mass the phosphorus content in the unsaturated urethane oligomer (A) can be made 1% by mass or more.
  • the polyol component (A1) having a phosphorus content exceeding 10% by mass can be used, the compatibility with other components may be lowered, and the compatibility can be reduced by setting the phosphorus content to 10% by mass or less. It can be set as a favorable polyol component (A1).
  • the polyol (a1) is a polyol having 2 to 3 hydroxyl groups per molecule and a hydroxyl value of 35 to 150 mgKOH / g and having a phosphorus atom in the molecule.
  • a polyol (a1) may be used individually by 1 type, and may use 2 or more types together.
  • the polyol (a1) can be obtained as a commercial product.
  • “FC450” (number of hydroxyl groups: 2, hydroxyl value: 450 mgKOH / g, phosphorus content: 7.2 mass%) manufactured by Adeka Corporation, “Weston 430” manufactured by Weston Chemical Co., Ltd. (number of hydroxyl groups: 3, hydroxyl value: 395 mg KOH / g, phosphorus content: 12.0 mass%)
  • “Nonen R0412-15” manufactured by Maruhishi Oil Chemical Co., Ltd.
  • the number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, and 2 is preferable. If the number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
  • the hydroxyl value of the polyol (a1) is 35 to 150 mgKOH / g, preferably 40 to 145 mgKOH / g. If the hydroxyl value of the polyol (a1) is 35 mgKOH / g or more, the molecular weight of the polyol (a1) does not become too large, so that the viscosity of the polyol (a1) does not become too large, and there is no problem in workability. When the hydroxyl value of the polyol (a1) is 145 mgKOH / g or less, the compatibility with the monomer (B) is improved and the transparency of the cured product is improved. The hydroxyl value of the polyol (a1) is measured according to JIS K1557-1 (2007 edition). The same applies to the hydroxyl value of other polyols.
  • the polyol (a2) is a polyoxyalkylene polyol having 2 hydroxyl groups per molecule and a hydroxyl value of 20 to 120 mgKOH / g and having no phosphorus atom in the molecule.
  • the polyol (a2) is a polyol having a polyoxyalkylene chain comprising an oxyalkylene group, and is preferably a polyoxyalkylene polyol obtained by ring-opening addition polymerization of a monoepoxide as an initiator in the presence of a catalyst.
  • a polyol (a2) may be used individually by 1 type, and may use 2 or more types together.
  • the catalyst examples include diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex, cesium compound, alkali (earth) metal compound and the like, and double metal cyanide complex is preferable.
  • a polyoxyalkylene polyol having a low hydroxyl value is obtained by reacting propylene oxide with a general-purpose alkali metal compound catalyst (potassium hydroxide, etc.)
  • the isomerization reaction of propylene oxide easily occurs and the degree of unsaturation increases.
  • a cured product containing an unsaturated urethane oligomer (A) obtained using a polyoxyalkylene polyol having a high degree of unsaturation may have insufficient mechanical properties.
  • the unsaturation degree of the polyol (a2) is preferably 0.05 meq / g or less.
  • the double metal cyanide complex a complex mainly composed of zinc hexacyanocobaltate is preferable, and an ether and / or alcohol complex of zinc hexacyanocobaltate is particularly preferable.
  • the ether and / or alcohol complex of zinc hexacyanocobaltate include those described in JP-B-46-27250.
  • the ether ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether and the like are preferable, and glyme is particularly preferable from the viewpoint of easy handling at the time of producing the complex.
  • the alcohol tert-butanol, tert-butyl cellosolve and the like are preferable.
  • the number of active hydrogens in the initiator is 2.
  • the active hydrogen means an active hydrogen atom that can react with a monoepoxide, such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group.
  • a monoepoxide such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group.
  • a hydrogen atom of a hydroxyl group is preferable. Therefore, a polyhydroxy compound having 2 hydroxyl groups is preferable as the initiator.
  • the initiator examples include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and a polyol (a2) obtained by reacting these with alkylene oxide And lower molecular weight polyoxyalkylene polyols.
  • the molecular weight of the initiator is preferably 500 to 1,500.
  • An initiator may be used individually by 1 type and may use 2 or more types together.
  • Monoepoxide is a compound having one epoxy ring.
  • the monoepoxide include alkylene oxide, glycidyl ether, glycidyl ester and the like, and alkylene oxide is preferable.
  • the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and the like, and ethylene oxide and propylene oxide are preferable.
  • a monoepoxide may be used individually by 1 type and may use 2 or more types together. When two or more kinds of monoepoxides are used in combination, any polymerization method of block polymerization and random polymerization may be used, and both block polymerization and random polymerization may be combined.
  • the polyol (a2) is preferably a polyoxypropylene polyol obtained using only propylene oxide as a monoepoxide, or a poly (oxypropylene / oxyethylene) polyol obtained using propylene oxide and a small amount of ethylene oxide as a monoepoxide.
  • Examples of the polyoxyalkylene polyol other than the polyoxyalkylene polyol obtained by reacting a monoepoxide with an initiator include polyoxytetramethylene polyol.
  • the number of hydroxyl groups per molecule of polyol (a2) is 2. If the number of hydroxyl groups per molecule of the polyol (a2) is 2, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
  • the hydroxyl value of the polyol (a2) is 20 to 120 mgKOH / g. If the hydroxyl value is within this range, the molecular weight of the polyol (a2) is not too large and the viscosity can be suppressed, which is industrially useful.
  • the hydroxyl value of the polyol (a2) is 20 mgKOH / g or more, the compatibility with the polyol (a1) is good, and the cured product obtained by curing the curable composition has sufficient transparency.
  • the hydroxyl value of the polyol (a2) is 120 mgKOH / g or less, the compatibility with the monomer (B) and the like is good, and the cured product has sufficient transparency.
  • the proportion of the polyol (a2) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass.
  • the proportion of the polyol (a2) is preferably 0.2 to 4 mol, more preferably 0.4 to 2.5 mol, relative to 1 mol of the polyol (a1). If the ratio of a polyol (a2) is this range, it can be compatible with transparency and flame retardance of the hardened
  • the polyol (a3) is a polyol that is neither the polyol (a1) nor the polyol (a2).
  • Examples of the polyol (a3) include polyoxyalkylene polyols having 3 or more hydroxyl groups.
  • polyols such as a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, are mentioned.
  • the polyol (a3) is not an essential component, and the proportion of the polyol (a3) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass.
  • the mass ratio in a polyol component (A1) shall be a small quantity.
  • the proportion of the polyol (a3) is preferably 25% by mass or less, more preferably 10% by mass or less, out of 100% by mass of the polyol component (A1).
  • the polyisocyanate compound (A2) is obtained by modifying alicyclic polyisocyanates, aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates having an average number of isocyanate groups of 2 or more per molecule, and aromatic ring-containing aliphatic polyisocyanates. Examples thereof include modified polyisocyanates.
  • An aromatic polyisocyanate having an isocyanate group bonded to an aromatic ring is preferably not used because it has a high possibility of causing yellowing of a cured product.
  • the average number of isocyanate groups per molecule of the polyisocyanate compound (A2) is preferably 2 to 4, and 2 is particularly preferable. That is, as the polyisocyanate compound (A2), diisocyanate is preferable.
  • a polyisocyanate compound (A2) may be used individually by 1 type, and may use 2 or more types together.
  • polyisocyanate compound (A2) examples include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, a prepolymer modified product, a nurate modified product, a urea modified product, and a carbodiimide modified product of the diisocyanate. And isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.
  • the unsaturated hydroxy compound (A3) is a compound having a curable functional group and a hydroxyl group, and two or more curable functional groups may be present in one molecule, and two or more hydroxyl groups are present in one molecule. It may be.
  • a compound having one curable functional group and one hydroxyl group per molecule is preferred.
  • the unsaturated hydroxy compound (A3) is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 10 carbon atoms, more preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 5 carbon atoms.
  • the curable functional group is preferably an acryloyloxy group. Therefore, the unsaturated hydroxy compound (A3) is more preferably a hydroxyalkyl acrylate having a hydroxyalkyl having 1 to 5 carbon atoms.
  • the unsaturated hydroxy compound (A3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, and the like.
  • 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred, Hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferred.
  • An unsaturated hydroxy compound (A3) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition of the present invention is a composition containing an unsaturated urethane oligomer (A).
  • the curable resin composition sandwiched between a pair of transparent substrates, which will be described later, is cured to form a transparent laminate. It is suitable as a curable resin composition used in the production method.
  • the curable resin composition containing the unsaturated urethane oligomer (A) can be used for adhesives, coating agents, and other applications.
  • Various additives can be added to the curable resin composition depending on the application. It is usually essential to add a curing agent for curing the curable resin composition, and a radical generator or a photopolymerization initiator is preferable as the curing agent.
  • a curable resin composition containing a curing agent that generates radicals by heat is a thermosetting type
  • a curable resin composition containing a photopolymerization initiator is a photocurable type.
  • the curable resin composition containing the unsaturated urethane oligomer (A) monomers such as a monomer (B) and other monomers (F) described later are blended for adjusting the physical properties of the cured product. It is preferable.
  • a monomer a compound having 1 to 6 curable functional groups is preferable, and a compound having 1 to 2 curable functional groups is more preferable. From the viewpoint of obtaining a hard cured product, a compound having 3 to 6 curable functional groups is preferred.
  • a low viscosity compound is preferable as a monomer from the point which improves the applicability
  • Various additives that do not participate in the reaction may be added to the curable resin composition.
  • this additive the below-mentioned additive (G) etc. are mentioned, for example.
  • the curable resin composition is applied using a solvent, and then the curable resin composition is cured by removing the solvent.
  • no solvent is used.
  • the curable resin composition used in the method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates according to the present invention comprises an unsaturated urethane oligomer (A) as an essential component. It is preferable that the monomer (B), the monomer (C), the photopolymerization initiator (D), and / or other unsaturated oligomers (E) are further contained, and if necessary, other monomers
  • the body (F), additive (G), etc. may further be included.
  • the unsaturated urethane oligomer (A) is preferably added so that the phosphorus content in the curable resin composition (100% by mass) is 0.1 to 5% by mass, and 0.1 to 3% by mass. It is more preferable to add so that it becomes. If phosphorus content is 0.1 mass% or more, the hardened
  • the unsaturated urethane oligomer (A) is preferably 10 to 100 parts by mass, more preferably 40 to 60 parts by mass, out of a total of 100 parts by mass of the components (A) to (C), (E) and (F). If unsaturated urethane oligomer (A) is 10 mass parts or more, the flame retardance of hardened
  • the monomer (C) When the monomer (C) is included, 3 to 50 parts by mass is preferable, and 5 to 25 parts by mass is preferable among 100 parts by mass in total of the components (A) to (C), (E) and (F). More preferred. If the ratio of a monomer (C) is 3 mass parts or more, the softness
  • oligomer (E) When other oligomer (E) is included, 3 to 55 parts by mass is preferable, and 30 to 50 parts by mass is preferable among 100 parts by mass of the total of components (A) to (C), (E) and (F). More preferred. When the ratio of the other oligomer (E) is 3 parts by mass or more, the flexibility of the cured product is improved and the viscosity of the curable resin composition can be lowered, which is industrially useful. When other monomer (F) is included, 50 parts by mass or less is preferable and 100 parts by mass or less is preferable among the total 100 parts by mass of components (A) to (C), (E) and (F). More preferred. When the additive (G) is included, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C), (E) and (F). .
  • the monomer (B) is a compound represented by CH 2 ⁇ C (R) C (O) O—R 2 (where R is a hydrogen atom or a methyl group, and R 2 has 1 to 2 hydroxyl groups) And a hydroxyalkyl group having 3 to 4 carbon atoms.
  • the monomer (B) is effective as a component that increases the hydrophilicity of the cured product of the curable resin composition and improves the affinity between the cured product and the surface of the transparent substrate (glass plate). By using (B), the adhesion between the cured product and the transparent substrate is improved.
  • the monomer (B) is a (meth) acrylate having a hydroxyalkyl group or a dihydroxyalkyl group, and is preferably a methacrylate in order to proceed the reaction with the unsaturated urethane oligomer (A) uniformly. That is, even if the curable functional group of the unsaturated urethane oligomer (A) is an acryloyloxy group, the reactivity is low, and if the curable functional group of the monomer (B) is an acryloyloxy group, both curable functional groups There is a possibility that a difference in reactivity between groups becomes large and uniform curing cannot be obtained.
  • a monomer (B) may be used individually by 1 type, and may use 2 or more types together.
  • the number of hydroxyl groups of the monomer (B) is 2 or less, the cured product is hardly brittle. Accordingly, the number of hydroxyl groups in R 2 is 1 to 2, and more preferably 1.
  • the number of carbon atoms in R 2 of the monomer (B) is 3-4.
  • R 2 has 3 or more carbon atoms, the compatibility with the unsaturated urethane oligomer (A) having a long chain structure is good, and a cured product obtained by curing the curable composition has sufficient transparency.
  • the carbon number of R 2 is 4 or less, the hydroxyl group density becomes high and sufficient adhesion can be obtained.
  • Examples of the monomer (B) include 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like, and 2-hydroxybutyl methacrylate is preferable.
  • the monomer (C) is a compound represented by CH 2 ⁇ C (R) C (O) O—R 3 (wherein R is a hydrogen atom or a methyl group, and R 3 has 8 to 22 carbon atoms) It is an alkyl group of
  • the monomer (C) is preferably methacrylate, but the monomer (C) has a higher molecular weight than the monomer (B), so it may be An acrylate may also be used.
  • a monomer (C) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition contains the monomer (C)
  • the elastic modulus of the cured product is lowered, and the tear resistance is easily improved.
  • carbon number of an alkyl group is 8 or more, there is little volatility and the glass transition temperature of hardened
  • the carbon number of the alkyl group is 22 or less, the alcohol component of the raw material can be easily obtained via a natural product and is more industrial.
  • Examples of the monomer (C) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate and the like, and n-dodecyl methacrylate and n-octadecyl methacrylate are particularly preferable.
  • Photopolymerization initiator (D) When the curable resin composition of this invention contains a photoinitiator (D), it becomes a photocurable resin composition.
  • the photopolymerization initiator (D) those which are excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and are activated to accelerate the curing reaction are preferable.
  • photopolymerization initiator (D) examples include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzoin isobutyl ether, benzoin Isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, such as 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2- Hydro Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan
  • An acyl phosphine oxide-based photopolymerization initiator such as bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide is particularly preferable from the viewpoint of curing the conductive resin composition.
  • a photoinitiator (D) may be used individually by 1 type, and may use 2 or more types together.
  • the curable resin composition of the present invention may contain a small amount of an unsaturated oligomer (E) other than the unsaturated urethane oligomer (A) for the purpose of adjusting the viscosity of the composition and the physical properties of the cured product.
  • unsaturated oligomers (E) include urethane (meth) acrylate oligomers obtained using polyols that do not contain phosphorus atoms, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like. Can be mentioned.
  • the curable resin composition of the present invention is a monomer (F) ((meth) acrylate other than the monomer (B) and the monomer (C) for the purpose of adjusting the physical properties of the resulting cured product. Etc.) may be included in a small amount.
  • the other monomer (F) include poly (meth) acrylate of polyhydric alcohol.
  • the curable resin composition contains a low boiling point compound.
  • the method of injecting and curing a liquid curable resin composition between a pair of transparent substrates sealed at the periphery even when injecting with a reduced pressure between the transparent substrates, it is exposed to a reduced pressure at the time of injection. Since the surface area of the curable resin composition is narrow and the degree of vacuum need not be so high, volatilization is a problem even if the curable resin composition contains a compound having a relatively low boiling point. There are few.
  • the curable resin composition is exposed to reduced pressure in a state where the curable resin composition spreads over almost the entire surface excluding the peripheral portion of the transparent substrate.
  • the disappearance due to volatilization is severe, and the composition of the curable resin composition may change greatly.
  • the monomer (B) is a hydroxyalkyl (meth) acrylate and has a sufficiently high boiling point. Further, the monomer (C) has a higher boiling point than the alkyl group having a large number of carbon atoms, even if it is an alkyl (meth) acrylate. Alkyl (meth) acrylates having a low carbon number of the alkyl group often have a low boiling point, and the curable resin composition containing such a low boiling point alkyl (meth) acrylate as another monomer (F) is: It cannot be used as a curable resin composition for producing a transparent laminate by a reduced pressure lamination method.
  • the curable resin composition that can be used in the reduced pressure lamination method preferably does not contain a monomer having a normal pressure boiling point of 150 ° C. or lower, preferably 200 ° C. or lower.
  • additive (G) examples include ultraviolet absorbers (benzotriazoles, hydroxyphenyltriazines, etc.), light stabilizers (hindered amines, etc.), pigments, dyes, metal oxide fine particles, fillers, and the like.
  • the viscosity of the curable resin composition used in the method for producing a transparent laminate likewise the viscosity of the present invention curable resin composition which can be used in other applications, the viscosity V 40 at 40 ° C. It is preferably 50 Pa ⁇ s or less.
  • the viscosity V 25 at 25 ° C. is preferably 0.05 Pa ⁇ s or more.
  • the viscosity is measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U).
  • V 40 When the viscosity V 40 is 50 Pa ⁇ s or less, the fluidity is good, and when used in the reduced pressure laminating method described later, bubbles that do not easily disappear in the curable resin composition are hardly generated.
  • the curable resin composition is used for an application in which a solvent can be used, the solvent is added to increase fluidity to perform application, etc., and then the curable resin composition obtained by removing the solvent is cured. Can be made.
  • V 25 of the curable resin composition is 0.05 Pa ⁇ s or more, the physical properties of the cured product are improved.
  • the specific unsaturated urethane oligomer (A) obtained by using the specific polyol component (A1) described above Therefore, when the composition is cured, a cured product having excellent transparency and flame retardancy is obtained.
  • the curable resin composition of the present invention is preferably used as a curable resin composition for producing a transparent laminate described later.
  • the present invention is not limited to this application, and can be used for other applications as a curable resin, particularly as a photocurable resin.
  • An example of such a laminate is a solar cell module.
  • at least one substrate is transparent so that light necessary for curing the photocurable resin composition can be incident thereon.
  • thermosetting resin composition can be used for thermosetting, but even if the opaque substrate is opaque to visible light, for example against ultraviolet rays necessary for photocuring. If it is transparent, a photocurable resin composition can be used even if both surfaces are opaque substrates.
  • a transparent substrate with low light transmittance a glass substrate on which a thin film solar cell is formed is used, and a layer made of a cured product of the curable resin composition of the present invention is formed between the glass substrate and a solar cell module.
  • a layer made of a cured product of the curable resin composition of the present invention is formed between the glass substrate and a solar cell module.
  • cured material of the curable resin composition of this invention a flame retardance performance can be provided to a solar cell module, and safety
  • a power generation layer made of thin film silicon can be provided on both glass substrates, or a thin film silicon substrate and a glass substrate on which a compound semiconductor thin film is formed can be combined and laminated.
  • both substrates such as a glass substrate may be transparent.
  • a plurality of solar cell substrates made of single crystal silicon or microcrystalline silicon are arranged between a pair of glass substrates, and the solar cell substrate is interposed between the glass substrates by a cured product of the curable resin composition of the present invention. It can also be enclosed.
  • One side of the glass substrate may be a waterproof resin sheet.
  • Such a solar cell module has flame retardancy, and safety is improved when it is installed in a building.
  • even if a part of the solar cell substrate to be encapsulated is defective and excessive current flows to generate heat, it is encapsulated by using the cured product of the curable resin composition of the present invention as the encapsulating resin. Since the resin has flame retardancy, safety can be improved.
  • the transparent laminate of the present invention has a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates.
  • this transparent laminated body and this transparent substrate mean that it is transparent with respect to visible light.
  • the transparent substrate examples include a glass plate or a resin plate. If a glass plate is used, a laminated glass is obtained. If a polycarbonate plate is used as the resin plate, a lightweight transparent panel having high impact resistance can be obtained. Further, a glass plate and a resin plate may be used in combination.
  • the size of the transparent substrate is not particularly limited, but can be widely used as a transparent member to be installed in an opening for a building or a vehicle if it is a transparent substrate having at least one side of 300 mm or more, more preferably 600 mm or more. . In normal applications, a size of 4 m 2 or less is appropriate.
  • the layer of the cured resin contained in the transparent laminate is a layer made of a cured product of the curable resin composition of the present invention.
  • the thickness of the cured resin layer is preferably 0.2 to 4.0 mm. When the thickness of the cured resin layer is 0.2 mm or more, the mechanical strength of the transparent laminate is good. When the thickness of the cured resin layer is 4.0 mm or less, the transparent laminate is excellent in transparency and can be used as a window glass.
  • the cured resin layer sandwiched between the transparent substrates is made of a cured product of the curable resin composition of the present invention, and thus has excellent transparency and flame retardancy. Excellent in properties.
  • the transparent laminate of the present invention can be produced by a known production method (for example, a method of sandwiching a curable resin composition between a pair of transparent substrates and curing the curable resin composition). It is preferable to manufacture by a reduced pressure lamination method using a curable resin composition.
  • the decompression lamination method itself is described in International Publication No. 2008/081838 and International Publication No. 2009/016943.
  • the feature of the reduced pressure lamination method is that a curable resin composition layer is formed on one transparent substrate, and another transparent substrate is stacked on the curable resin composition layer in a reduced pressure atmosphere.
  • the curable resin composition is hermetically sealed between the transparent substrates and then placed in a pressure atmosphere (usually an atmospheric pressure atmosphere) higher than the reduced-pressure atmosphere to cure the curable resin composition.
  • a pressure atmosphere usually an atmospheric pressure atmosphere
  • 1st process The said hardening which formed the sealed space which accommodated the curable resin composition inside between a pair of transparent substrates in a pressure-reduced atmosphere, and was sealed between a pair of transparent substrates and this pair of transparent substrates.
  • 2nd process The process of putting the said lamination
  • the reduced pressure atmosphere in the first step is preferably a pressure atmosphere of 1 kPa or less, and more preferably a pressure atmosphere of 100 Pa or less. Further, if the pressure in the reduced-pressure atmosphere is too low, the curable resin composition such as a monomer may be volatilized. Therefore, the reduced-pressure atmosphere is preferably a pressure atmosphere of 1 Pa or more, and more preferably a pressure atmosphere of 10 Pa or more.
  • the atmosphere having a higher pressure than the reduced-pressure atmosphere in the second step is preferably a pressure atmosphere of 50 kPa or more, and more preferably a pressure atmosphere of 100 kPa or more.
  • the pressure atmosphere in the second step is usually an atmospheric pressure atmosphere.
  • the production method will be described by taking as an example the case where the atmosphere having a higher pressure than the reduced pressure atmosphere is an atmospheric pressure atmosphere.
  • the bubbles are likely to disappear before the curable resin composition is cured, and a cured resin layer having no bubbles is easily obtained.
  • the laminated precursor formed in the first step is placed under atmospheric pressure, pressure is also applied to the curable resin composition in the sealed space due to the pressure from the transparent substrate under atmospheric pressure.
  • the inside of the bubbles in the curable resin composition is at the reduced-pressure atmospheric pressure in the first step, the volume of the bubbles is reduced by the pressure applied to the curable resin composition in the second step. When this gas dissolves in the curable resin composition, the bubbles disappear.
  • the lamination precursor In order to eliminate bubbles, it is preferable to hold the lamination precursor under atmospheric pressure for a while before the curable resin composition is cured.
  • the holding time is preferably 5 minutes or more, but the holding time may be shorter when there are no bubbles or when the bubbles are very small and quickly disappear.
  • the reduced pressure atmosphere is required at the stage of forming the sealed space, and is not required at the stage before that.
  • a sealing material having a predetermined thickness is provided around the periphery of one surface of one transparent substrate, and the curable resin composition is supplied to the surface of the transparent substrate in a region surrounded by the sealing material to be curable.
  • these steps can be performed in an atmospheric pressure atmosphere.
  • the sealed space is preferably formed as follows.
  • the transparent substrate having the layer of the curable resin composition obtained as described above and the other transparent substrate are put in a reduced pressure chamber and set in a predetermined arrangement. That is, a transparent substrate having a layer of a curable resin composition was placed on a horizontal surface plate with the layer of the curable resin composition facing up, and the other transparent substrate was attached to the tip of a cylinder that could be moved up and down. It attaches to the lower surface of a horizontal surface plate, and both transparent substrates are located in parallel, without making the layer of curable resin composition contact the other transparent substrate. Thereafter, the decompression chamber is closed and evacuated, and the inside of the decompression chamber is set to a predetermined decompressed atmosphere.
  • the cylinder After the inside of the decompression chamber becomes a predetermined decompression atmosphere, the cylinder is operated and both transparent substrates are overlapped via the layer of the curable resin composition, and the curable resin is placed in the space surrounded by the both transparent substrates and the sealing material. The composition is sealed to form a laminated precursor. After forming the lamination precursor, the inside of the reduced pressure chamber is returned to the atmospheric pressure atmosphere, and the lamination precursor is taken out from the reduced pressure chamber.
  • the adhesion strength between the transparent substrates and the sealing material may be such that no gas enters from the interface between the transparent substrate and the sealing material when the laminated precursor is placed under atmospheric pressure.
  • a layer of a pressure sensitive adhesive can be provided on the surface of the sealing material to adhere the transparent substrate and the sealing material.
  • a curable adhesive is provided at the interface between the transparent substrate and the sealing material, or the sealing material is formed of a curable resin to form a laminated precursor, and then taken out from the vacuum chamber or from the vacuum chamber. Thereafter, the adhesive strength between the transparent substrate and the sealing material can be increased by curing the curable adhesive or the curable resin.
  • the second step is a step of placing the lamination precursor under atmospheric pressure and curing the curable resin composition.
  • the curable resin composition is a thermosetting curable resin, it is thermoset. More preferably, a photocurable resin composition is used as the curable resin composition and photocured. Photocuring can be performed by irradiating light from a light source such as an ultraviolet lamp through a transparent substrate. The light irradiation is preferably performed for 3 to 30 minutes. As described above, it is preferable to harden the curable resin composition after holding the laminated precursor for a while under atmospheric pressure. By curing the curable resin composition, the curable resin composition becomes a cured resin, and the transparent laminate as described above is obtained.
  • Examples 1 to 12 are examples, and examples 13 to 16 are comparative examples.
  • the phosphorus content in each sample was measured by atomic absorption spectrometry using an inductively coupled plasma emission spectrophotometer (Seiko Instruments, SPS3100).
  • the transmittance was measured as an evaluation of the transparency of the portion where the cured resin layer of the transparent laminate was present.
  • the transmittance was measured according to ASTM D1003 using Hazeguard II (manufactured by Toyo Seiki Seisakusho).
  • the transmittance of the transparent laminate is preferably 90% or more from the viewpoint of clear visibility when used as a laminated glass, for example.
  • the temperature chamber was heated so that the temperature profile was almost the same as the temperature profile defined by the Cabinet Order of Article 109-2 of the Building Standards Act, Article 2, Item 9 of the Building Standards Act.
  • the case where no flame was generated from the non-heated surface was evaluated as “pass”; the case where the flame was generated from the non-heated surface was determined as “fail”.
  • Polyol (c-4) “Nonen R0811-9” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 142 mgKOH / g, phosphorus content: 12.0% by mass).
  • Polyol (a2) Polyol (d-1): Zinc hexacyanocobaltate-glyme complex was used as a catalyst, propylene oxide was reacted with an initiator to deactivate the catalyst, and then potassium hydroxide was used as a catalyst to react with ethylene oxide. The catalyst was deactivated and purified to obtain a polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 28 mgKOH / g, oxyethylene group ratio: 24% by mass).
  • Polyol (d-2) Polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 112 mgKOH / g) was obtained by reacting propylene oxide with an initiator using potassium hydroxide as a catalyst and purifying.
  • Polyol component (A1) Polyols (c-1) to (c-5) and polyols (d-1) to (d-2) are mixed in the molar ratio shown in Table 1 to obtain polyol components (b-1) to (b-8). ) The phosphorus content in the polyol components (b-1) to (b-8) was measured. The results are shown in Table 1. Further, the hues of the polyol components (b-1) to (b-8) were observed. The results are shown in Table 1.
  • Example 1 To 100 parts by mass (0.05 mol) of the polyol component (b-3), 15.5 parts by mass (0.1 mol) of isophorone diisocyanate (hereinafter referred to as IPDI) is added, and dibutyltin dilaurate (hereinafter referred to as DBTDL). In the presence of 0.01 part by mass of (A), the reaction was carried out at 80 ° C. for 4 hours to obtain a urethane prepolymer.
  • IPDI isophorone diisocyanate
  • DBTDL dibutyltin dilaurate
  • urethane prepolymer 0.05 part by mass of DBTDL and 0.05 part by mass of hydroquinone monomethyl ether (hereinafter referred to as HQME) were added, and 2-hydroxyethyl acrylate (hereinafter referred to as HEA) at 50 ° C. 8.0 parts by mass (0.1 mol) was added, stirred at 60 ° C., and the reaction was carried out until the isocyanate groups disappeared while measuring the isocyanate group content by NCO titration according to JIS K1603-1. A urethane acrylate oligomer (e-1) was obtained.
  • HQME hydroquinone monomethyl ether
  • urethane acrylate oligomer e-1
  • HBMA 2-hydroxybutyl methacrylate
  • DMA n-dodecyl methacrylate
  • HCHPK 1-hydroxycyclohexyl phenyl ketone
  • Example 2 A urethane acrylate oligomer (e-2) was obtained in the same manner as in Example 1 except that the polyol (b-4) was used in place of the polyol (b-3) to prepare a photocurable resin composition.
  • Example 3 7.5 parts by weight (0.065 moles) of IPDI is added to 100 parts by weight (0.05 moles) of polyol (b-5) and reacted at 80 ° C. for 4 hours in the presence of 0.01 parts by weight of DBTDL.
  • DBTDL 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C.
  • Example 4 A urethane acrylate oligomer (e-4) was obtained in the same manner as in Example 3 except that the polyol (b-6) was used instead of the polyol (b-5) to prepare a photocurable resin composition.
  • Example 5 To 100 parts by mass (0.05 mol) of polyol (b-6), 10 parts by mass (0.06 mol) of IPDI was added and reacted at 80 ° C. for 4 hours in the presence of 0.01 part by mass of DBTDL. A urethane prepolymer was obtained. Add 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME to the urethane prepolymer, add 5.0 parts by mass (0.02 mol) of HEA at 50 ° C, and stir at 60 ° C.
  • Example 6 10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HBMA, and 50 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
  • Example 7 80 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 8 1 part by mass of HCHPK was added to 100 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 to prepare a photocurable resin composition.
  • Example 9 A urethane acrylate oligomer (e-6) was obtained in the same manner as in Example 4 except that the polyol (b-7) was used instead of the polyol (b-6), and the photocurable resin was obtained in the same manner as in Example 6. A composition was prepared.
  • Example 10 80 parts by mass of the urethane acrylate oligomer (e-6) obtained in Example 9 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 11 7.0 parts by mass (0.065 mol) of hexamethylene diisocyanate (hereinafter referred to as HDI) is added to 100 parts by mass (0.05 mol) of polyol (b-6), and 0.01 parts by mass of DBTDL is added. Was reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer.
  • 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C.
  • urethane acrylate oligomer (e-7) While measuring the isocyanate group content by NCO titration according to K1603-1, the reaction was carried out until the isocyanate group disappeared to obtain a urethane acrylate oligomer (e-7). 10 parts by mass of urethane acrylate oligomer (e-7), 40 parts by mass of HBMA, 50 parts by mass of urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, 1 part by mass of HCHPK was added, and light A curable resin composition was prepared.
  • Example 12 10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of 2-hydroxypropyl methacrylate (hereinafter referred to as HPMA), the urethane acrylate oligomer (e-8) obtained in Example 13 ) And 1 part by mass of HCHPK were added to prepare a photocurable resin composition.
  • HPMA 2-hydroxypropyl methacrylate
  • HCHPK 2-hydroxypropyl methacrylate
  • Example 13 A urethane acrylate oligomer (e-8) was obtained in the same manner as in Example 1 except that the polyol (b-8) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-8), 40 parts by mass of HPMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 14 5 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HPMA, and 55 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
  • Example 15 A urethane acrylate oligomer (e-9) was obtained in the same manner as in Example 1 except that the polyol (b-1) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-9), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • Example 16 A urethane acrylate oligomer (e-10) was obtained in the same manner as in Example 1 except that the polyol (b-2) was used instead of the polyol (b-3). 40 parts by mass of urethane acrylate oligomer (e-10), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
  • soda lime glass As a transparent substrate, two pieces of soda lime glass having a length of 610 mm, a width of 610 mm, and a thickness of 2 mm were prepared. After sticking a double-sided adhesive tape (seal material) having a thickness of 1 mm and a width of 10 mm along the edges of the four sides of one transparent substrate, the release film on the upper surface of the double-sided adhesive tape was removed.
  • a double-sided adhesive tape adhesive material
  • An ultraviolet curable resin for sealing prepared by uniformly mixing 100 parts by mass of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., product name “UF8001G”) and 1 part by mass of benzoin isopropyl ether (polymerization initiator) in advance
  • a coating thickness of about 0.3 mm was applied with a dispenser to form an ultraviolet curable resin layer for sealing.
  • the curable resin composition was dropped at a plurality of locations using a dispenser in a region surrounded by the double-sided adhesive tape on the surface of the transparent substrate on which the double-sided adhesive tape was applied, so that the total mass was 380 g.
  • the transparent substrate 10 in which the curable resin composition 14 was dropped in a region surrounded by the double-sided adhesive tape 12 (sealing material) was placed horizontally in the decompression chamber 26.
  • the other transparent substrate 16 is held on the upper surface plate 30 in the decompression chamber 26 by using the suction pad 32, is opposed to the transparent substrate 10 in parallel, and the distance from the transparent substrate 10 is 10 mm. .
  • the decompression chamber 26 was sealed, and the vacuum pump 28 was operated to evacuate the interior of the decompression chamber 26 to about 30 Pa. At this time, foaming of the curable resin composition 14 did not continue.
  • the upper platen 30 was lowered by the cylinder 34, and the transparent substrate 10 and the transparent substrate 16 were pressure-bonded with a pressure of 2 kPa and held for 1 minute.
  • the inside of the decompression chamber 26 was returned to atmospheric pressure in about 30 seconds, and a laminated precursor in which the transparent substrate 10 and the transparent substrate 16 were in close contact with each other through the uncured layer of the curable resin composition 14 was obtained.
  • the upper surface plate 30 was raised by the cylinder 34, and the laminated precursor adhered to the suction pad 32 of the upper surface plate 30 was peeled from the upper surface plate 30.
  • the ultraviolet curable resin 36 was cured. Thereafter, the laminated precursor was kept horizontal and allowed to stand for about 1 hour.
  • a transparent laminate (laminated glass) is obtained by curing the curable resin composition 14 by irradiating ultraviolet rays having an intensity of 1 mW / cm 2 for 10 minutes uniformly from both sides of the laminate precursor with a high-pressure mercury lamp. Obtained.
  • the evaluation results of the transparent laminate are shown in Table 3 and Table 4.
  • the transparent laminates of Examples 1 to 12 using a curable resin composition having a phosphorus content of 0.1% by mass or more had good flame retardancy and good transparency.
  • the transparent laminated bodies of Examples 13 and 14 used a curable resin composition having a phosphorus content of less than 0.1% by mass, the flame retardancy was insufficient.
  • the curable resin compositions of Examples 15 and 16 since the hydroxyl value of the polyol (a1) was high, the urethane acrylate oligomer and the monomer were not compatible. Therefore, in Examples 15 and 16, the transparent laminate was not manufactured.
  • a transparent laminate was obtained in the same manner by replacing DMA used in Examples with n-octadecyl methacrylate. Results similar to those shown in Table 2 were obtained.
  • the curable resin composition of the present invention is useful as a raw material for the adhesive resin layer of laminated glass, and the transparent laminate of the present invention includes laminated glass (windshield glass, safety glass, security glass, fire safety glass, etc.), It is useful for displays, solar cell modules and the like.
  • laminated glass windshield glass, safety glass, security glass, fire safety glass, etc.

Abstract

Provided are a transparent laminate which is highly transparent and has excellent flame retardancy and a process for producing the laminate. A curable resin composition (14) containing an unsaturated urethane oligomer (A) which has 2-4 curable functional groups per molecule on average and is a product of the reaction of (A1) a polyol ingredient that comprises (a1) a polyol having 2-3 hydroxy groups per molecule, a hydroxyl value of 35-150 mg-KOH/g, and a phosphorus atom in the molecule and has a phosphorus content of 1-7 mass%, (A2) a polyisocyanate compound, and (A3) an unsaturated hydroxy compound having the curable functional group (X) shown below and a hydroxy group is held between a pair of transparent substrates (10, 16) and is cured to obtain a transparent laminate. The curable functional group (X) is a group represented by the formula CH2=C(R)C(O)O- (wherein R is a hydrogen atom or methyl).

Description

不飽和ウレタンオリゴマー、硬化性樹脂組成物、透明積層体およびその製造方法Unsaturated urethane oligomer, curable resin composition, transparent laminate and method for producing the same
　本発明は、一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に好適な難燃性の不飽和ウレタンオリゴマー、該不飽和ウレタンオリゴマーを含む硬化性樹脂組成物、該硬化性樹脂組成物の硬化物からなる硬化樹脂の層を有する透明積層体、および該硬化性樹脂組成物を用いた透明積層体の製造方法に関する。 The present invention relates to a flame retardant unsaturated urethane oligomer suitable for a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates, and a curing containing the unsaturated urethane oligomer. The present invention relates to a curable resin composition, a transparent laminate having a cured resin layer composed of a cured product of the curable resin composition, and a method for producing a transparent laminate using the curable resin composition.
　一対の透明基板と、該透明基板の間に挟まれた接着性樹脂層を有する透明積層体としては、一対のガラス板を、接着性樹脂層を介して一体化した合わせガラスが知られている。該合わせガラスは、破損したガラス破片がフィルム状の接着性樹脂層に付着して飛散しないことから自動車の風防ガラスとして用いられている。また、該合わせガラスは、貫通し難く強度が優れていることから、建物の窓ガラス（安全ガラス、防犯ガラス、防火安全ガラス等）として用いられている。したがって、窓ガラスとして用いる場合、接着性樹脂層には、透明性に優れるほかに、難燃性が良好であることが要求されることがある。 As a transparent laminate having a pair of transparent substrates and an adhesive resin layer sandwiched between the transparent substrates, a laminated glass in which a pair of glass plates are integrated via an adhesive resin layer is known. . The laminated glass is used as a windshield for automobiles because broken glass fragments adhere to the film-like adhesive resin layer and do not scatter. Further, the laminated glass is used as a window glass for buildings (safety glass, crime prevention glass, fire prevention safety glass, etc.) because it is difficult to penetrate and has excellent strength. Therefore, when used as a window glass, the adhesive resin layer may be required to have good flame retardance in addition to excellent transparency.
　防火安全ガラスは、火災時には防火戸として機能し、平常時には安全ガラスとして機能するガラスである。通常、合わせガラスの接着性樹脂層に用いる樹脂材料は、その分解温度に達すると徐々に低分子量物質に熱分解する。揮発性物質にまで分解する温度が、生成する揮発性物質の着火温度より高い場合には着火し発火する。したがって、防火安全ガラス用の接着性樹脂層の樹脂材料には、分解生成物の酸化反応を抑制する樹脂材料、分解生成物が生成してもそれが揮発しにくい樹脂材料、熱分解と同時に架橋反応や環化反応を起こして炭化する樹脂材料、すなわち、難燃性の高い樹脂材料を用いる必要がある。 Fireproof safety glass is a glass that functions as a fire door during a fire and functions as a safety glass during normal times. Usually, the resin material used for the adhesive resin layer of laminated glass gradually decomposes into low molecular weight substances when the decomposition temperature is reached. If the temperature that decomposes into volatile substances is higher than the ignition temperature of the volatile substances that are generated, it will ignite and ignite. Therefore, the resin material of the adhesive resin layer for fire safety safety glass includes a resin material that suppresses the oxidation reaction of the decomposition product, a resin material that does not volatilize even if the decomposition product is generated, and is crosslinked simultaneously with thermal decomposition. It is necessary to use a resin material that carbonizes by causing a reaction or a cyclization reaction, that is, a resin material having high flame retardancy.
　接着性樹脂層の樹脂材料として難燃性能の高い樹脂材料を用いた合わせガラスとしては、下記のものが提案されている。
　（１）接着性樹脂層の樹脂材料として含フッ素共重合体を用いた防火安全ガラス（特許文献１）。
　（２）接着性樹脂層の樹脂材料にリン系難燃剤を添加した合わせガラス（特許文献２）。 The following are proposed as laminated glass using a resin material having high flame retardancy as the resin material of the adhesive resin layer.
(1) Fire safety glass using a fluorine-containing copolymer as a resin material for the adhesive resin layer (Patent Document 1).
(2) Laminated glass obtained by adding a phosphorus-based flame retardant to the resin material of the adhesive resin layer (Patent Document 2).
　しかし、（１）の防火安全ガラスでは、難燃性が向上する半面、ガラス板と接着性樹脂層との密着性が不充分になる。そのため、ヘイズ値が高くなり、窓ガラスとして用いることは困難である。
　（２）の合わせガラスでは、接着性樹脂層の樹脂材料にリン系難燃剤が均一に混ざりにくいため、透明性が損なわれたり、難燃性が不均一となったりする。また、難燃性を発現するためには、リン系難燃剤の添加量を多くする必要がある。しかし、リン系難燃剤の添加量が多いと、接着性樹脂層の強度等の機械的特性が損なわれたり、添加した難燃剤が経時的に接着性樹脂層の内部で移動するなどして耐久性に問題が発生したりする。 However, in the fireproof safety glass (1), the flame retardance is improved, but the adhesion between the glass plate and the adhesive resin layer is insufficient. Therefore, a haze value becomes high and it is difficult to use it as a window glass.
In the laminated glass of (2), since the phosphorus-based flame retardant is not easily mixed with the resin material of the adhesive resin layer, the transparency is impaired or the flame retardancy is not uniform. Moreover, in order to express a flame retardance, it is necessary to increase the addition amount of a phosphorus flame retardant. However, if the amount of phosphorus-based flame retardant added is large, the mechanical properties such as the strength of the adhesive resin layer are impaired, or the added flame retardant migrates inside the adhesive resin layer over time. Problems occur.
　なお、難燃性が期待される樹脂材料としては、リン含有の難燃性ポリオールを原料に用いたウレタンプレポリマー組成物が開示されている（特許文献３）。
　しかし、該ウレタンプレポリマー組成物は、合わせガラスの接着性樹脂層に用いる場合には耐久性が懸念される。 In addition, as a resin material expected to be flame retardant, a urethane prepolymer composition using a phosphorus-containing flame retardant polyol as a raw material is disclosed (Patent Document 3).
However, when this urethane prepolymer composition is used for the adhesive resin layer of laminated glass, there is a concern about durability.
　また、合わせガラスの製造方法としては、下記の方法が知られている。
　（ｉ）一対の透明基板の間に接着性樹脂フィルムを挟み、この積層物を加熱圧着して合わせガラスを製造する方法。
　（ii）周辺をシールした一対の透明基板の間に液状の硬化性樹脂を注入した後、硬化性樹脂を硬化して合わせガラスを製造する方法（特許文献４）。 Moreover, the following method is known as a manufacturing method of a laminated glass.
(I) A method of producing a laminated glass by sandwiching an adhesive resin film between a pair of transparent substrates and thermocompression bonding the laminate.
(Ii) A method of manufacturing a laminated glass by injecting a liquid curable resin between a pair of transparent substrates whose periphery is sealed, and then curing the curable resin (Patent Document 4).
　（ii）の方法は、（ｉ）の方法に比べ、硬化性樹脂のバリエーションが広く、目的に応じて種々の物性の硬化物を得やすいこと、硬化容易な硬化性樹脂（特に光硬化性樹脂）を用いることにより製造プロセスを簡略化できる等の特徴を有する。
　しかし、（ii）の方法は、硬化性樹脂の注入に際し、樹脂中に気泡が残存しやすいという欠点を有する。 The method (ii) has a wider variety of curable resins than the method (i), and it is easy to obtain a cured product having various physical properties according to the purpose, and an easily curable resin (especially a photocurable resin). ) Can be used to simplify the manufacturing process.
However, the method (ii) has a drawback that bubbles tend to remain in the resin when the curable resin is injected.
　気泡の発生を防ぐ方法としては、減圧積層方法が知られている。減圧積層方法による合わせガラスの製造方法としては、たとえば、下記の方法が知られている。
　（iii）一枚の透明基板上に光硬化性樹脂組成物の層を形成し、減圧下にもう一枚の透明基板を該光硬化性樹脂組成物の層の上に重ねて、一対の透明基板の間に光硬化性樹脂組成物を密閉した後、大気圧下で該光硬化性樹脂組成物を光硬化させる合わせガラスの製造方法（特許文献５）。 As a method for preventing the generation of bubbles, a vacuum lamination method is known. For example, the following method is known as a method for producing laminated glass by the reduced pressure lamination method.
(Iii) A layer of the photocurable resin composition is formed on one transparent substrate, and another transparent substrate is stacked on the layer of the photocurable resin composition under reduced pressure to form a pair of transparent A method for producing a laminated glass, in which a photocurable resin composition is sealed between substrates and then photocured under atmospheric pressure (Patent Document 5).
　光硬化性樹脂組成物としては、不飽和ウレタンオリゴマーを含む光硬化性樹脂組成物が提案されている（特許文献５）。また、（iii）の方法に適した光硬化性樹脂組成物としても、不飽和ウレタンオリゴマーを含む光硬化性樹脂組成物が知られている（特許文献６）。
　不飽和ウレタンオリゴマーを含む光硬化性樹脂組成物においては、不飽和ウレタンオリゴマーや各種のモノマー類を併用することにより、硬化物の特性を調整できる。しかし、従来の光硬化性樹脂組成物では、難燃性が良好な硬化物を得ることができない。 As a photocurable resin composition, a photocurable resin composition containing an unsaturated urethane oligomer has been proposed (Patent Document 5). Moreover, the photocurable resin composition containing an unsaturated urethane oligomer is known also as a photocurable resin composition suitable for the method of (iii) (patent document 6).
In the photocurable resin composition containing an unsaturated urethane oligomer, the characteristics of the cured product can be adjusted by using an unsaturated urethane oligomer and various monomers in combination. However, the conventional photocurable resin composition cannot obtain a cured product having good flame retardancy.
特開平０８－１３２５６０号公報Japanese Patent Laid-Open No. 08-132560 特開２００７－２６１８３７号公報JP 2007-261837 A 特開平１１－２６３９０６号公報Japanese Patent Laid-Open No. 11-263906 特開２００５－０４１７４７号公報JP 2005-041747 A 国際公開第２００８／０８１８３８号International Publication No. 2008/081838 国際公開第２００９／０１６９４３号International Publication No. 2009/016943
　本発明は、透明性に優れ、かつ難燃性に優れる硬化物を得ることができる不飽和ウレタンオリゴマーおよび硬化性樹脂組成物を提供する。また、透明積層体を製造する方法に用いられる硬化性樹脂組成物を提供する。さらに、透明性に優れ、かつ難燃性に優れる透明積層体およびその製造方法を提供する。 The present invention provides an unsaturated urethane oligomer and a curable resin composition capable of obtaining a cured product having excellent transparency and flame retardancy. Moreover, the curable resin composition used for the method of manufacturing a transparent laminated body is provided. Furthermore, the transparent laminated body which is excellent in transparency and excellent in a flame retardance, and its manufacturing method are provided.
　本発明は、下記［１］～［１５］の発明である。
　［１］下記ポリオール成分（Ａ１）と、ポリイソシアネート化合物（Ａ２）と、下記不飽和ヒドロキシ化合物（Ａ３）との反応生成物であって、下記硬化性官能基を１分子あたり平均２～４個有し、リン含有量が１～７質量％である、不飽和ウレタンオリゴマー（Ａ）。
　ポリオール成分（Ａ１）：下記ポリオール（ａ１）を含むポリオール成分。
　ポリオール（ａ１）：１分子あたりの水酸基数が２～３であり、水酸基価が３５～１５０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有するポリオール。
　不飽和ヒドロキシ化合物（Ａ３）：下記硬化性官能基と水酸基とを有する化合物。
　硬化性官能基：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは、水素原子またはメチル基である）。 The present invention is the following [1] to [15].
[1] A reaction product of the following polyol component (A1), polyisocyanate compound (A2), and unsaturated hydroxy compound (A3) shown below, and an average of 2 to 4 curable functional groups shown below per molecule An unsaturated urethane oligomer (A) having a phosphorus content of 1 to 7% by mass.
Polyol component (A1): A polyol component containing the following polyol (a1).
Polyol (a1): A polyol having 2 to 3 hydroxyl groups per molecule, a hydroxyl value of 35 to 150 mgKOH / g, and having a phosphorus atom in the molecule.
Unsaturated hydroxy compound (A3): A compound having the following curable functional group and hydroxyl group.
Curable functional group: CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
　［２］前記ポリオール成分（Ａ１）が、下記ポリオール（ａ２）をさらに含む、［１］の不飽和ウレタンオリゴマー（Ａ）。
　ポリオール（ａ２）：１分子あたりの水酸基数が２であり、水酸基価が２０～１２０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有さないポリオキシアルキレンポリオール。 [2] The unsaturated urethane oligomer (A) of [1], wherein the polyol component (A1) further comprises the following polyol (a2).
Polyol (a2): A polyoxyalkylene polyol having 2 hydroxyl groups per molecule and a hydroxyl value of 20 to 120 mgKOH / g and having no phosphorus atom in the molecule.
　［３］［１］または［２］の不飽和ウレタンオリゴマー（Ａ）を含む、硬化性樹脂組成物。
　［４］一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物である、［３］の硬化性樹脂組成物。
　［５］下記単量体（Ｂ）をさらに含む、［４］の硬化性樹脂組成物。
　単量体（Ｂ）：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ２で表される化合物（ただし、Ｒは、水素原子またはメチル基であり、Ｒ２は、水酸基数が１～２であり、炭素数が３～４のヒドロキシアルキル基である）。 [3] A curable resin composition comprising the unsaturated urethane oligomer (A) of [1] or [2].
[4] The curable resin composition according to [3], which is a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates.
[5] The curable resin composition according to [4], further including the following monomer (B).
Monomer (B): a compound represented by CH 2 ═C (R) C (O) O—R 2 (wherein R is a hydrogen atom or a methyl group, and R 2 has a hydroxyl number of 1 to 2 and a hydroxyalkyl group having 3 to 4 carbon atoms).
　［６］下記単量体（Ｃ）をさらに含む、［４］または［５］の硬化性樹脂組成物。
　単量体（Ｃ）：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ３で表される化合物（ただし、Ｒは、水素原子またはメチル基であり、Ｒ３は、炭素数が８～２２のアルキル基である）。
　［７］光重合開始剤（Ｄ）をさらに含む、［４］～［６］の硬化性樹脂組成物。
　［８］硬化性樹脂組成物（１００質量％）中のリン含有量が、０．１～５質量％である、［４］～［７］の硬化性樹脂組成物。 [6] The curable resin composition of [4] or [5], further comprising the following monomer (C).
Monomer (C): Compound represented by CH 2 ═C (R) C (O) O—R 3 (wherein R is a hydrogen atom or a methyl group, and R 3 has 8 to 8 carbon atoms) 22 alkyl groups).
[7] The curable resin composition of [4] to [6], further comprising a photopolymerization initiator (D).
[8] The curable resin composition according to [4] to [7], wherein the phosphorus content in the curable resin composition (100% by mass) is 0.1 to 5% by mass.
　［９］一対の透明基板と、該透明基板の間に挟まれた硬化樹脂の層とを有する透明積層体であって、前記硬化樹脂が、［４］～［８］の硬化性樹脂組成物の硬化物である、透明積層体。
　［１０］前記一対の透明基板の少なくとも一方が、ガラス板である、［９］の透明積層体。 [9] A transparent laminate having a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates, wherein the cured resin is a curable resin composition of [4] to [8] A transparent laminate that is a cured product of the above.
[10] The transparent laminate according to [9], wherein at least one of the pair of transparent substrates is a glass plate.
　［１１］減圧雰囲気中で、一対の透明基板間に、［４］～［８］の硬化性樹脂組成物を内部に収容した密閉空間を形成して、一対の透明基板と該一対の透明基板間に密閉された前記硬化性樹脂組成物とを有する積層前駆体を製造する第１の工程と、前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる第２の工程とを有する、透明積層体の製造方法。
　［１２］前記減圧雰囲気が１００Ｐａ以下の圧力雰囲気であり、前記減圧雰囲気よりも圧力が高い雰囲気が大気圧雰囲気である、［１１］の製造方法。
　［１３］前記硬化性樹脂組成物が光硬化性樹脂組成物であり、第２の工程において前記積層前駆体に光を照射して前記硬化性樹脂組成物を硬化させる、［１１］または［１２］の製造方法。 [11] A pair of transparent substrates and the pair of transparent substrates are formed between the pair of transparent substrates in a reduced-pressure atmosphere by forming a sealed space in which the curable resin composition of [4] to [8] is accommodated. A first step of producing a laminated precursor having the curable resin composition sealed in between, and the laminated precursor is placed in an atmosphere having a pressure higher than the reduced-pressure atmosphere, and the curing is performed in the atmosphere. The manufacturing method of a transparent laminated body which has a 2nd process of hardening an adhesive resin composition.
[12] The method according to [11], wherein the reduced-pressure atmosphere is a pressure atmosphere of 100 Pa or less, and the atmosphere having a higher pressure than the reduced-pressure atmosphere is an atmospheric pressure atmosphere.
[13] The curable resin composition is a photocurable resin composition, and in the second step, the laminated precursor is irradiated with light to cure the curable resin composition. [11] or [12 ] Manufacturing method.
　［１４］下記硬化性官能基を１分子あたり平均２～４個有し、リン含有量が１～７質量％である、不飽和ウレタンオリゴマー（Ａ）。
　硬化性官能基：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは、水素原子またはメチル基である）。
　［１５］［１４］の不飽和ウレタンオリゴマー（Ａ）を含む、硬化性樹脂組成物。 [14] An unsaturated urethane oligomer (A) having an average of 2 to 4 curable functional groups described below per molecule and a phosphorus content of 1 to 7% by mass.
Curable functional group: CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
[15] A curable resin composition comprising the unsaturated urethane oligomer (A) of [14].
　本発明の不飽和ウレタンオリゴマーによれば、透明性に優れ、かつ難燃性に優れる硬化物を得ることができる。
　本発明の硬化性樹脂組成物によれば、透明性に優れ、かつ難燃性に優れる硬化物を得ることができる。
　本発明の透明積層体は、透明性に優れ、かつ難燃性に優れる。
　本発明の透明積層体の製造方法によれば、透明性に優れ、かつ難燃性に優れる透明積層体を製造できる。 According to the unsaturated urethane oligomer of the present invention, a cured product having excellent transparency and flame retardancy can be obtained.
According to the curable resin composition of the present invention, a cured product having excellent transparency and flame retardancy can be obtained.
The transparent laminate of the present invention is excellent in transparency and flame retardancy.
According to the method for producing a transparent laminate of the present invention, a transparent laminate having excellent transparency and excellent flame retardancy can be produced.
透明積層体の製造における一工程を示す断面図である。It is sectional drawing which shows 1 process in manufacture of a transparent laminated body.
　本明細書におけるＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは水素原子またはメチル基である。）で表される硬化性官能基は、アクリロイルオキシ基（Ｒが水素原子の場合）またはメタクリロイルオキシ基（Ｒがメチル基の場合）であり、以下に該式で表される基を（メタ）アクリロイルオキシ基ともいう。同様に、「アクリレート」と「メタクリレート」の総称として、「（メタ）アクリレート」を用いる。 In this specification, the curable functional group represented by CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group) is an acryloyloxy group (where R is a hydrogen atom). Or a methacryloyloxy group (when R is a methyl group), and the group represented by the formula is also referred to as a (meth) acryloyloxy group. Similarly, “(meth) acrylate” is used as a general term for “acrylate” and “methacrylate”.
　＜不飽和ウレタンオリゴマー＞
　本発明の不飽和ウレタンオリゴマー（Ａ）は、下記硬化性官能基を１分子あたり平均２～４個有し、リン含有量が１～６質量％のウレタン（メタ）アクリレートオリゴマーである。
　硬化性官能基：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは、水素原子またはメチル基である）。 <Unsaturated urethane oligomer>
The unsaturated urethane oligomer (A) of the present invention is a urethane (meth) acrylate oligomer having an average of 2 to 4 curable functional groups described below per molecule and a phosphorus content of 1 to 6% by mass.
Curable functional group: CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
　不飽和ウレタンオリゴマー（Ａ）は、一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物の一成分として好適なものである。不飽和ウレタンオリゴマー（Ａ）は、分子中にリン原子を有するため、硬化物は難燃性を有する。 The unsaturated urethane oligomer (A) is suitable as one component of a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates. It is. Since the unsaturated urethane oligomer (A) has a phosphorus atom in the molecule, the cured product has flame retardancy.
　不飽和ウレタンオリゴマー（Ａ）の１分子あたりの平均硬化性官能基数は、２～４であり、２～３が好ましい。平均硬化性官能基数が２以上であれば、硬化樹脂層の一部に架橋構造を導入でき、耐熱性が増し、高温にさらされた場合に硬化樹脂層が流動変形しにくい。平均硬化性官能基数が４以下であれば、架橋密度が大きくなり過ぎず、硬化樹脂層の柔軟性が良好になり、耐衝撃性が良好になる。 The average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is 2 to 4, and preferably 2 to 3. If the average number of curable functional groups is 2 or more, a crosslinked structure can be introduced into a part of the cured resin layer, heat resistance is increased, and the cured resin layer is less likely to flow and deform when exposed to high temperatures. If the average number of curable functional groups is 4 or less, the crosslink density will not be too high, the flexibility of the cured resin layer will be good, and the impact resistance will be good.
　不飽和ウレタンオリゴマー（Ａ）の１分子あたりの平均硬化性官能基数は、後述するポリオール成分（Ａ１）の水酸基数、ポリイソシアネート化合物（Ａ２）のイソシアネート基数、不飽和ヒドロキシ化合物（Ａ３）の硬化性官能基数および水酸基数により調整される。ポリイソシアネート化合物（Ａ２）としてはイソシアネート基数が２であるジイソシアネートが好ましいこと、不飽和ヒドロキシ化合物（Ａ３）としては硬化性官能基数が１である不飽和モノオールが好ましいことから、これらを用いて得られる不飽和ウレタンオリゴマー（Ａ）の１分子あたりの平均硬化性官能基数は、通常、ポリオール成分（Ａ１）１分子あたりの平均水酸基数とほぼ同じとなる。たとえば、ポリオール成分（Ａ１）としてジオールのみを用いることにより１分子あたりの平均硬化性官能基数が２の不飽和ウレタンオリゴマー（Ａ）が得られる。同様に、ポリオール成分（Ａ１）としてジオールとトリオールを用いることにより平均硬化性官能基数が２と３の間の数の不飽和ウレタンオリゴマー（Ａ）が得られ、ポリオール成分（Ａ１）としてトリオールのみを用いることにより平均硬化性官能基数が３の不飽和ウレタンオリゴマー（Ａ）が得られる。 The average number of curable functional groups per molecule of the unsaturated urethane oligomer (A) is the number of hydroxyl groups of the polyol component (A1), the number of isocyanate groups of the polyisocyanate compound (A2), and the curability of the unsaturated hydroxy compound (A3). It is adjusted by the number of functional groups and the number of hydroxyl groups. Diisocyanate having 2 isocyanate groups is preferable as the polyisocyanate compound (A2), and unsaturated monool having 1 curable functional group is preferable as the unsaturated hydroxy compound (A3). The average number of curable functional groups per molecule of the obtained unsaturated urethane oligomer (A) is usually substantially the same as the average number of hydroxyl groups per molecule of the polyol component (A1). For example, by using only a diol as the polyol component (A1), an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 can be obtained. Similarly, by using diol and triol as the polyol component (A1), an unsaturated urethane oligomer (A) having an average curable functional group number between 2 and 3 is obtained, and only triol is obtained as the polyol component (A1). When used, an unsaturated urethane oligomer (A) having an average number of curable functional groups of 3 is obtained.
　１分子中に複数存在する硬化性官能基は、同一でもあってもよく、異なっていてもよい。しかし、通常は、１分子中に複数の硬化性官能基を有する場合には、同一の硬化性官能基あることが好ましい。
　不飽和ウレタンオリゴマー（Ａ）中の硬化性官能基は、アクリロイルオキシ基であることが好ましい。不飽和ウレタンオリゴマー（Ａ）中の硬化性官能基は、不飽和ウレタンオリゴマー（Ａ）が高分子量であるほど反応性が低くなりやすく、相対的に低分子量の化合物と併用した場合、両者の硬化性官能基の反応性の差を少なくするためには、不飽和ウレタンオリゴマー（Ａ）中の硬化性官能基の反応性は高いことが好ましい。そのため、不飽和ウレタンオリゴマー（Ａ）中の硬化性官能基としては、メタクリロイルオキシ基よりも反応性の高いアクリロイルオキシ基が好ましい。 A plurality of curable functional groups present in one molecule may be the same or different. However, usually, when having a plurality of curable functional groups in one molecule, it is preferable that they have the same curable functional group.
The curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group. The curable functional group in the unsaturated urethane oligomer (A) tends to be less reactive as the unsaturated urethane oligomer (A) has a higher molecular weight, and when used in combination with a relatively low molecular weight compound, both cure. In order to reduce the difference in the reactivity of the functional group, it is preferable that the reactivity of the curable functional group in the unsaturated urethane oligomer (A) is high. Therefore, the curable functional group in the unsaturated urethane oligomer (A) is preferably an acryloyloxy group having a higher reactivity than the methacryloyloxy group.
　不飽和ウレタンオリゴマー（Ａ）（１００質量％）中のリン含有量は、１～７質量％であり、１～４質量％が好ましい。リン含有量が１質量％以上であれば、充分な難燃効果を得ることができる。リン含有量が７質量％以下であれば、不飽和ウレタンオリゴマー（Ａ）製造時における、オリゴマーの高分子量化（ゲル化）や、相溶性の低下による不均質なオリゴマーの生成がなく、また硬化性組成物を硬化して得られる硬化物が充分な透明性を有するため、好ましい。 The phosphorus content in the unsaturated urethane oligomer (A) (100% by mass) is 1 to 7% by mass, preferably 1 to 4% by mass. When the phosphorus content is 1% by mass or more, a sufficient flame retardant effect can be obtained. When the phosphorus content is 7% by mass or less, there is no generation of heterogeneous oligomers due to high molecular weight (gelation) of oligomers or lowering of compatibility during the production of unsaturated urethane oligomer (A), and curing. Since the cured | curing material obtained by hardening | curing an adhesive composition has sufficient transparency, it is preferable.
　不飽和ウレタンオリゴマー（Ａ）は、ポリオール成分（Ａ１）とポリイソシアネート化合物（Ａ２）と不飽和ヒドロキシ化合物（Ａ３）との反応生成物であり、該反応生成物を得る方法としては、たとえば、下記（１）～（３）の方法が挙げられる。
　（１）ポリオール成分（Ａ１）、ポリイソシアネート化合物（Ａ２）および不飽和ヒドロキシ化合物（Ａ３）を同時反応させる方法。
　（２）ポリイソシアネート化合物（Ａ２）と不飽和ヒドロキシ化合物（Ａ３）とを化学量論的にイソシアネート基が過剰の条件で反応させた後、得られた反応物にさらにポリオール成分（Ａ１）を反応させる方法。
　（３）ポリオール成分（Ａ１）とポリイソシアネート化合物（Ａ２）とを化学量論的にイソシナネート基が過剰の条件で反応させた後、得られた反応物にさらに不飽和ヒドロキシ化合物（Ａ３）を反応させる方法。 The unsaturated urethane oligomer (A) is a reaction product of the polyol component (A1), the polyisocyanate compound (A2), and the unsaturated hydroxy compound (A3). Examples of a method for obtaining the reaction product include the following: Examples thereof include the methods (1) to (3).
(1) A method in which a polyol component (A1), a polyisocyanate compound (A2), and an unsaturated hydroxy compound (A3) are simultaneously reacted.
(2) After reacting the polyisocyanate compound (A2) and the unsaturated hydroxy compound (A3) in a stoichiometrically excessive condition with an isocyanate group, the resulting reaction product is further reacted with a polyol component (A1). How to make.
(3) After reacting the polyol component (A1) and the polyisocyanate compound (A2) in a stoichiometrically excessive condition with an isocyanate group being excessive, the resulting reaction product is further reacted with an unsaturated hydroxy compound (A3). How to make.
　（１）の方法は、容易であるが、不飽和ウレタンオリゴマー（Ａ）の分子量や粘度にばらつきが見られやすく、工業的に好ましくない。
　（２）の方法は、ポリオール成分（Ａ１）の水酸基数が３以上の場合に、超高分子量生成物（ゲル成分）が生成しにくい。
　（３）の方法は、定常的に定性的な不飽和ウレタンオリゴマー（Ａ）を得ることができるため、工業的に好ましい。 Although the method (1) is easy, variations in the molecular weight and viscosity of the unsaturated urethane oligomer (A) are easily observed, which is not industrially preferable.
In the method (2), when the number of hydroxyl groups in the polyol component (A1) is 3 or more, an ultrahigh molecular weight product (gel component) is hardly generated.
The method (3) is industrially preferable because a qualitative unsaturated urethane oligomer (A) can be obtained constantly.
　（３）の方法としては、下記の工程（３－１）、工程（３－２）を有する方法が挙げられる。
　（３－１）必要に応じてウレタン化触媒の存在下、ポリオール成分（Ａ１）とポリイソシアネート化合物（Ａ２）を化学量論的にイソシアネート基が過剰な条件で反応させ、イソシアネート基末端ウレタンプレポリマーを得る工程。
　（３－２）必要に応じて重合禁止剤の存在下、不飽和ヒドロキシ化合物（Ａ３）をウレタンプレポリマーの末端のイソシアネート基と反応させる工程。 Examples of the method (3) include a method having the following step (3-1) and step (3-2).
(3-1) If necessary, the polyol component (A1) and the polyisocyanate compound (A2) are reacted in the presence of a stoichiometric excess of isocyanate groups in the presence of a urethanization catalyst to obtain an isocyanate group-terminated urethane prepolymer. Obtaining.
(3-2) A step of reacting the unsaturated hydroxy compound (A3) with an isocyanate group at the terminal of the urethane prepolymer in the presence of a polymerization inhibitor as necessary.
　工程（３－１）：
　ウレタン化触媒としては、ナフテン酸コバルト、ナフテン酸亜鉛、２－エチルヘキサン酸亜鉛、ジブチル錫ジラウレート、２－エチルヘキサン酸錫、トリエチルアミン、１，４－ジアビシクロ［２．２．２］オクタン等が挙げられる。
　ポリオール成分（Ａ１）とポリイソシアネート化合物（Ａ２）との割合は、イソシアネート基：水酸基のモル比が１．２：１～３：１となる割合が好ましく、１．２：１～２：１となる割合がより好ましい。反応温度は、通常のウレタン化反応における温度、すなわち３０～９０℃が好ましい。 Step (3-1):
Examples of urethanization catalysts include cobalt naphthenate, zinc naphthenate, zinc 2-ethylhexanoate, dibutyltin dilaurate, tin 2-ethylhexanoate, triethylamine, 1,4-diabicyclo [2.2.2] octane, and the like. It is done.
The ratio of the polyol component (A1) and the polyisocyanate compound (A2) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1.2: 1 to 3: 1, and is 1.2: 1 to 2: 1. Is more preferred. The reaction temperature is preferably a temperature in a normal urethanization reaction, that is, 30 to 90 ° C.
　工程（３－２）：
　重合禁止剤としては、ヒドロキノン、ヒドロキノンモノメチルエーテル、２，６－ジ－ｔｅｒｔ－ブチル－ヒドロキノン、ｏ－ニトロトルエン等が挙げられる。重合禁止剤の量は、不飽和ヒドロキシ化合物（Ａ３）に対して５０～５，０００ｐｐｍが好ましい。
　ウレタンプレポリマーと不飽和ヒドロキシ化合物（Ａ３）との割合は、イソシアネート基：水酸基のモル比が１：１～１：１．５となるような割合が好ましい。反応温度は、３０～９０℃が好ましい。 Step (3-2):
Examples of the polymerization inhibitor include hydroquinone, hydroquinone monomethyl ether, 2,6-di-tert-butyl-hydroquinone, o-nitrotoluene and the like. The amount of the polymerization inhibitor is preferably 50 to 5,000 ppm based on the unsaturated hydroxy compound (A3).
The ratio of the urethane prepolymer and the unsaturated hydroxy compound (A3) is preferably such that the molar ratio of isocyanate group: hydroxyl group is 1: 1 to 1: 1.5. The reaction temperature is preferably 30 to 90 ° C.
（ポリオール成分（Ａ１））
　ポリオール成分（Ａ１）は、分子中にリン原子を有するポリオール（ａ１）を必須成分として含むポリオール成分であり、ポリオール（ａ２）をさらに含むことが好ましく、必要に応じて他のポリオール（ａ３）を含んでいてもよい。 (Polyol component (A1))
The polyol component (A1) is a polyol component containing a polyol (a1) having a phosphorus atom in the molecule as an essential component, preferably further containing a polyol (a2), and if necessary, another polyol (a3). May be included.
　ポリオール成分（Ａ１）（１００質量％）中のリン含有量は、１質量％を超え、１０質量％以下が好ましく、１．１～８．５質量％がより好ましい。リン含有量が１質量％を超えるポリオール成分（Ａ１）を用いることにより不飽和ウレタンオリゴマー（Ａ）中のリン含有量を１質量％以上にすることができる。リン含有量が１０質量％を超えるポリオール成分（Ａ１）を用いることもできるが、他の成分との相溶性が低下するおそれがあり、リン含有量を１０質量％以下にすることにより相溶性の良好なポリオール成分（Ａ１）とすることができる。 The phosphorus content in the polyol component (A1) (100% by mass) is more than 1% by mass, preferably 10% by mass or less, and more preferably 1.1 to 8.5% by mass. By using the polyol component (A1) having a phosphorus content exceeding 1% by mass, the phosphorus content in the unsaturated urethane oligomer (A) can be made 1% by mass or more. Although the polyol component (A1) having a phosphorus content exceeding 10% by mass can be used, the compatibility with other components may be lowered, and the compatibility can be reduced by setting the phosphorus content to 10% by mass or less. It can be set as a favorable polyol component (A1).
（ポリオール（ａ１））
　ポリオール（ａ１）は、１分子あたりの水酸基数が２～３であり、水酸基価が３５～１５０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有するポリオールである。ポリオール（ａ１）は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Polyol (a1))
The polyol (a1) is a polyol having 2 to 3 hydroxyl groups per molecule and a hydroxyl value of 35 to 150 mgKOH / g and having a phosphorus atom in the molecule. A polyol (a1) may be used individually by 1 type, and may use 2 or more types together.
　ポリオール（ａ１）は、市販品として入手できる。該市販品としては、下記のものが挙げられる。
　アデカ社製の「ＦＣ４５０」（水酸基数：２、水酸基価：４５０ｍｇＫＯＨ／ｇ、リン含有量：７．２質量％）、
　ウェストンケミカル社製の「Ｗｅｓｔｏｎ４３０」（水酸基数：３、水酸基価：３９５ｍｇＫＯＨ／ｇ、リン含有量：１２．０質量％）、
　丸菱油化社製の「ノンネンＲ０４１２－１５」（水酸基数：２、水酸基価：４０ｍｇＫＯＨ／ｇ、リン含有量：１１．０質量％）、
　丸菱油化社製の「ノンネンＲ０８１１－９」（水酸基数：２、水酸基価：１４２ｍｇＫＯＨ／ｇ、リン含有量：１２．０質量％）、
　クラリアント社製の「ＯＰ５５０」（水酸基数：２、水酸基価：１４５ｍｇＫＯＨ／ｇ、リン含有量：１７．０質量％）等。 The polyol (a1) can be obtained as a commercial product. The following are mentioned as this commercial item.
“FC450” (number of hydroxyl groups: 2, hydroxyl value: 450 mgKOH / g, phosphorus content: 7.2 mass%) manufactured by Adeka Corporation,
“Weston 430” manufactured by Weston Chemical Co., Ltd. (number of hydroxyl groups: 3, hydroxyl value: 395 mg KOH / g, phosphorus content: 12.0 mass%),
“Nonen R0412-15” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 40 mgKOH / g, phosphorus content: 11.0% by mass),
“Nonen R0811-9” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 142 mgKOH / g, phosphorus content: 12.0% by mass),
“OP550” manufactured by Clariant (hydroxyl number: 2, hydroxyl value: 145 mg KOH / g, phosphorus content: 17.0% by mass), etc.
　ポリオール（ａ１）の１分子あたりの水酸基数は、２～３であり、２が好ましい。ポリオール（ａ１）の１分子あたりの水酸基数が２～３であれば、１分子あたりの平均硬化性官能基数が２～４の不飽和ウレタンオリゴマー（Ａ）が容易に得られる。 The number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, and 2 is preferable. If the number of hydroxyl groups per molecule of the polyol (a1) is 2 to 3, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
　ポリオール（ａ１）の水酸基価は、３５～１５０ｍｇＫＯＨ／ｇであり、４０～１４５ｍｇＫＯＨ／ｇが好ましい。ポリオール（ａ１）の水酸基価が３５ｍｇＫＯＨ／ｇ以上であれば、ポリオール（ａ１）の分子量が大きくなりすぎないため、ポリオール（ａ１）の粘度が大きくなりすぎず、作業性に問題が生じない。ポリオール（ａ１）の水酸基価が１４５ｍｇＫＯＨ／ｇ以下であれば、単量体（Ｂ）との相溶性がよくなり、硬化物の透明性が良好となる。
　ポリオール（ａ１）の水酸基価は、ＪＩＳ　Ｋ１５５７－１（２００７年版）にしたがって測定する。他のポリオールの水酸基価も同様である。 The hydroxyl value of the polyol (a1) is 35 to 150 mgKOH / g, preferably 40 to 145 mgKOH / g. If the hydroxyl value of the polyol (a1) is 35 mgKOH / g or more, the molecular weight of the polyol (a1) does not become too large, so that the viscosity of the polyol (a1) does not become too large, and there is no problem in workability. When the hydroxyl value of the polyol (a1) is 145 mgKOH / g or less, the compatibility with the monomer (B) is improved and the transparency of the cured product is improved.
The hydroxyl value of the polyol (a1) is measured according to JIS K1557-1 (2007 edition). The same applies to the hydroxyl value of other polyols.
（ポリオール（ａ２））
　ポリオール（ａ２）は、１分子あたりの水酸基数が２であり、水酸基価が２０～１２０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有さないポリオキシアルキレンポリオールである。 (Polyol (a2))
The polyol (a2) is a polyoxyalkylene polyol having 2 hydroxyl groups per molecule and a hydroxyl value of 20 to 120 mgKOH / g and having no phosphorus atom in the molecule.
　ポリオール（ａ２）は、オキシアルキレン基からなるポリオキシアルキレン鎖を有するポリオールであり、触媒の存在下、開始剤にモノエポキシドを開環付加重合させて得られるポリオキシアルキレンポリオールであることが好ましい。
　ポリオール（ａ２）は、１種を単独で用いてもよく、２種以上を併用してもよい。 The polyol (a2) is a polyol having a polyoxyalkylene chain comprising an oxyalkylene group, and is preferably a polyoxyalkylene polyol obtained by ring-opening addition polymerization of a monoepoxide as an initiator in the presence of a catalyst.
A polyol (a2) may be used individually by 1 type, and may use 2 or more types together.
　触媒としては、ジエチル亜鉛、塩化鉄、金属ポルフィリン、複合金属シアン化物錯体、セシウム化合物、アルカリ（土類）金属化合物等が挙げられ、複合金属シアン化物錯体が好ましい。汎用のアルカリ金属化合物触媒（水酸化カリウム等）を用いてプロピレンオキシドを反応させて水酸基価の低いポリオキシアルキレンポリオールを得ると、プロピレンオキシドの異性化反応が起こりやすくなり、不飽和度が高くなる。不飽和度の高いポリオキシアルキレンポリオールを使用して得られる不飽和ウレタンオリゴマー（Ａ）を含む硬化物は機械的物性が不充分となるおそれがある。ポリオール（ａ２）の不飽和度は０．０５ｍｅｑ／ｇ以下が好ましい。 Examples of the catalyst include diethyl zinc, iron chloride, metal porphyrin, double metal cyanide complex, cesium compound, alkali (earth) metal compound and the like, and double metal cyanide complex is preferable. When a polyoxyalkylene polyol having a low hydroxyl value is obtained by reacting propylene oxide with a general-purpose alkali metal compound catalyst (potassium hydroxide, etc.), the isomerization reaction of propylene oxide easily occurs and the degree of unsaturation increases. . A cured product containing an unsaturated urethane oligomer (A) obtained using a polyoxyalkylene polyol having a high degree of unsaturation may have insufficient mechanical properties. The unsaturation degree of the polyol (a2) is preferably 0.05 meq / g or less.
　複合金属シアン化物錯体としては、亜鉛ヘキサシアノコバルテートを主成分とする錯体が好ましく、亜鉛ヘキサシアノコバルテートのエーテルおよび／またはアルコール錯体が特に好ましい。亜鉛ヘキサシアノコバルテートのエーテルおよび／またはアルコール錯体としては、特公昭４６－２７２５０号公報に記載のものが挙げられる。エーテルとしては、エチレングリコールジメチルエーテル（グライム）、ジエチレングリコールジメチルエーテル等が好ましく、錯体の製造時の取り扱いやすさの点から、グライムが特に好ましい。アルコールとしては、ｔｅｒｔ－ブタノール、ｔｅｒｔ－ブチルセロソルブ等が好ましい。 As the double metal cyanide complex, a complex mainly composed of zinc hexacyanocobaltate is preferable, and an ether and / or alcohol complex of zinc hexacyanocobaltate is particularly preferable. Examples of the ether and / or alcohol complex of zinc hexacyanocobaltate include those described in JP-B-46-27250. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether and the like are preferable, and glyme is particularly preferable from the viewpoint of easy handling at the time of producing the complex. As the alcohol, tert-butanol, tert-butyl cellosolve and the like are preferable.
　開始剤の活性水素数は、２である。活性水素とは、水酸基の水素原子、アミノ基の水素原子等、モノエポキシドが反応しうる活性な水素原子をいう。活性水素としては、水酸基の水素原子が好ましい。したがって、開始剤としては、水酸基数が２のポリヒドロキシ化合物が好ましい。開始剤としては、エチレングリコール、ジエチレングリコール、プロピレングリコール、ジプロピレングリコール、ネオペンチルグリコール、１，４－ブタンジオール、１，６－ヘキサンジオール、これらにアルキレンオキシドを反応させて得られる、ポリオール（ａ２）よりも低分子量のポリオキシアルキレンポリオール等が挙げられる。複合金属シアン化物錯体を用いる場合、開始剤の分子量は５００～１，５００が好ましい。開始剤は、１種を単独で用いてもよく、２種以上を併用してもよい。 The number of active hydrogens in the initiator is 2. The active hydrogen means an active hydrogen atom that can react with a monoepoxide, such as a hydrogen atom of a hydroxyl group or a hydrogen atom of an amino group. As the active hydrogen, a hydrogen atom of a hydroxyl group is preferable. Therefore, a polyhydroxy compound having 2 hydroxyl groups is preferable as the initiator. Examples of the initiator include ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, and a polyol (a2) obtained by reacting these with alkylene oxide And lower molecular weight polyoxyalkylene polyols. When a double metal cyanide complex is used, the molecular weight of the initiator is preferably 500 to 1,500. An initiator may be used individually by 1 type and may use 2 or more types together.
　モノエポキシドは、１個のエポキシ環を有する化合物である。モノエポキシドとしては、アルキレンオキシド、グリシジルエーテル、グリシジルエステル等が挙げられ、アルキレンオキシドが好ましい。アルキレンオキシドとしては、エチレンオキシド、プロピレンオキシド、１，２－ブチレンオキシド、２，３－ブチレンオキシド、スチレンオキシド等が挙げられ、エチレンオキシド、プロピレンオキシドが好ましい。モノエポキシドは、１種を単独で用いてもよく、２種以上を併用してもよい。モノエポキシドを２種以上併用する場合、ブロック重合およびランダム重合のいずれの重合法を用いてもよく、さらにブロック重合とランダム重合の両者を組み合わせてもよい。 Monoepoxide is a compound having one epoxy ring. Examples of the monoepoxide include alkylene oxide, glycidyl ether, glycidyl ester and the like, and alkylene oxide is preferable. Examples of the alkylene oxide include ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, styrene oxide, and the like, and ethylene oxide and propylene oxide are preferable. A monoepoxide may be used individually by 1 type and may use 2 or more types together. When two or more kinds of monoepoxides are used in combination, any polymerization method of block polymerization and random polymerization may be used, and both block polymerization and random polymerization may be combined.
　ポリオール（ａ２）としては、モノエポキシドとしてプロピレンオキシドのみを用いて得られるポリオキシプロピレンポリオール、またはモノエポキシドとしてプロピレンオキシドと少量のエチレンオキシドを用いて得られるポリ（オキシプロピレン・オキシエチレン）ポリオールが好ましい。
　開始剤にモノエポキシドを反応させて得られるポリオキシアルキレンポリオール以外のポリオキシアルキレンポリオールとしては、たとえば、ポリオキシテトラメチレンポリオールが挙げられる。 The polyol (a2) is preferably a polyoxypropylene polyol obtained using only propylene oxide as a monoepoxide, or a poly (oxypropylene / oxyethylene) polyol obtained using propylene oxide and a small amount of ethylene oxide as a monoepoxide.
Examples of the polyoxyalkylene polyol other than the polyoxyalkylene polyol obtained by reacting a monoepoxide with an initiator include polyoxytetramethylene polyol.
　ポリオール（ａ２）の１分子あたりの水酸基数は２である。ポリオール（ａ２）の１分子あたりの水酸基数が２であれば、１分子あたりの平均硬化性官能基数が２～４の不飽和ウレタンオリゴマー（Ａ）が容易に得られる。 The number of hydroxyl groups per molecule of polyol (a2) is 2. If the number of hydroxyl groups per molecule of the polyol (a2) is 2, an unsaturated urethane oligomer (A) having an average number of curable functional groups per molecule of 2 to 4 can be easily obtained.
　ポリオール（ａ２）の水酸基価は、２０～１２０ｍｇＫＯＨ／ｇである。水酸基価が該範囲であれば、ポリオール（ａ２）の分子量が大きすぎず、粘度も抑えることができるため、工業的に有用である。ポリオール（ａ２）の水酸基価が２０ｍｇＫＯＨ／ｇ以上では、ポリオール（ａ１）との相溶性が良好で、硬化性組成物を硬化して得られる硬化物が充分な透明性を有する。ポリオール（ａ２）の水酸基価が１２０ｍｇＫＯＨ／ｇ以下では、単量体（Ｂ）等との相溶性が良好で、硬化物が充分な透明性を有する。 The hydroxyl value of the polyol (a2) is 20 to 120 mgKOH / g. If the hydroxyl value is within this range, the molecular weight of the polyol (a2) is not too large and the viscosity can be suppressed, which is industrially useful. When the hydroxyl value of the polyol (a2) is 20 mgKOH / g or more, the compatibility with the polyol (a1) is good, and the cured product obtained by curing the curable composition has sufficient transparency. When the hydroxyl value of the polyol (a2) is 120 mgKOH / g or less, the compatibility with the monomer (B) and the like is good, and the cured product has sufficient transparency.
　ポリオール（ａ２）の割合は、ポリオール成分（Ａ１）（１００質量％）中のリン含有量は、１～７質量％となるように調製される。ポリオール（ａ２）の割合は、ポリオール（ａ１）の１モルに対して０．２～４モルが好ましく、０．４～２．５モルがより好ましい。ポリオール（ａ２）の割合が該範囲であれば、硬化性組成物を硬化して得られる硬化物の透明性と難燃性とを両立できる。ポリオール（ａ２）の割合が０．２モル以上では、単量体（Ｂ）との相溶性が良好で、硬化物が充分な透明性を有する。ポリオール（ａ２）の割合が４モル以下では、硬化物の難燃性が充分となる。 The proportion of the polyol (a2) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass. The proportion of the polyol (a2) is preferably 0.2 to 4 mol, more preferably 0.4 to 2.5 mol, relative to 1 mol of the polyol (a1). If the ratio of a polyol (a2) is this range, it can be compatible with transparency and flame retardance of the hardened | cured material obtained by hardening | curing a curable composition. When the ratio of the polyol (a2) is 0.2 mol or more, the compatibility with the monomer (B) is good, and the cured product has sufficient transparency. When the ratio of the polyol (a2) is 4 mol or less, the cured product has sufficient flame retardancy.
（ポリオール（ａ３））
　ポリオール（ａ３）は、ポリオール（ａ１）、ポリオール（ａ２）のいずれでもないポリオールである。ポリオール（ａ３）としては、たとえば、水酸基数が３以上のポリオキシアルキレンポリオール等が挙げられる。また、ポリエステルポリオール、ポリカプロラクトンポリオール、ポリカーボネートポリオール、ポリブタジエンポリオール等のポリオールが挙げられる。 (Polyol (a3))
The polyol (a3) is a polyol that is neither the polyol (a1) nor the polyol (a2). Examples of the polyol (a3) include polyoxyalkylene polyols having 3 or more hydroxyl groups. Moreover, polyols, such as a polyester polyol, a polycaprolactone polyol, a polycarbonate polyol, a polybutadiene polyol, are mentioned.
　ポリオール（ａ３）は必須成分ではなく、ポリオール（ａ３）の割合は、ポリオール成分（Ａ１）（１００質量％）中のリン含有量が１～７質量％となるように調製される。ポリオール（ａ３）を用いる場合はポリオール成分（Ａ１）中のその質量割合は少量とする。ポリオール（ａ３）の割合は、ポリオール成分（Ａ１）１００質量％のうち、２５質量％以下が好ましく、１０質量％以下がより好ましい。 The polyol (a3) is not an essential component, and the proportion of the polyol (a3) is adjusted so that the phosphorus content in the polyol component (A1) (100% by mass) is 1 to 7% by mass. When using a polyol (a3), the mass ratio in a polyol component (A1) shall be a small quantity. The proportion of the polyol (a3) is preferably 25% by mass or less, more preferably 10% by mass or less, out of 100% by mass of the polyol component (A1).
（ポリイソシアネート化合物（Ａ２））
　ポリイソシアネート化合物（Ａ２）としては、１分子あたりの平均イソシアネート基数が２以上の、脂環族系ポリイソシアネート、脂肪族系ポリイソシアネート、芳香環含有脂肪族系ポリイソシアネート、これらを変性して得られる変性ポリイソシアネート等が挙げられる。芳香環に結合したイソシアネート基を有する芳香族系ポリイソシアネートは、硬化物の黄変をもたらすおそれが大きいため、用いないことが好ましい。 (Polyisocyanate compound (A2))
The polyisocyanate compound (A2) is obtained by modifying alicyclic polyisocyanates, aliphatic polyisocyanates, aromatic ring-containing aliphatic polyisocyanates having an average number of isocyanate groups of 2 or more per molecule, and aromatic ring-containing aliphatic polyisocyanates. Examples thereof include modified polyisocyanates. An aromatic polyisocyanate having an isocyanate group bonded to an aromatic ring is preferably not used because it has a high possibility of causing yellowing of a cured product.
　ポリイソシアネート化合物（Ａ２）の１分子あたりの平均のイソシアネート基数は、２～４が好ましく、２が特に好ましい。すなわち、ポリイソシアネート化合物（Ａ２）としては、ジイソシアネートが好ましい。ポリイソシアネート化合物（Ａ２）は、１種を単独で用いてもよく、２種以上を併用してもよい。 The average number of isocyanate groups per molecule of the polyisocyanate compound (A2) is preferably 2 to 4, and 2 is particularly preferable. That is, as the polyisocyanate compound (A2), diisocyanate is preferable. A polyisocyanate compound (A2) may be used individually by 1 type, and may use 2 or more types together.
　ポリイソシアネート化合物（Ａ２）の具体例としては、イソホロンジイソシアネート、ジシクロヘキシルメタンジイソシアネート、ヘキサメチレンジイソシアネート、キシレンジイソシアネート等のジイソシアネート、該ジイソシアネートのプレポリマー変性体、ヌレート変性体、ウレア変性体、カルボジイミド変性体等が挙げられ、イソホロンジイソシアネート、ヘキサメチレンジイソシアネートが特に好ましい。 Specific examples of the polyisocyanate compound (A2) include diisocyanates such as isophorone diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate, xylene diisocyanate, a prepolymer modified product, a nurate modified product, a urea modified product, and a carbodiimide modified product of the diisocyanate. And isophorone diisocyanate and hexamethylene diisocyanate are particularly preferable.
（不飽和ヒドロキシ化合物（Ａ３））
　不飽和ヒドロキシ化合物（Ａ３）は、硬化性官能基と水酸基とを有する化合物であり、１分子中に硬化性官能基が２以上存在していてもよく、１分子中に水酸基が２以上存在していてもよい。硬化性官能基を１分子あたり平均２～４個有する不飽和ウレタンオリゴマー（Ａ）を製造するためには、１分子中に硬化性官能基と水酸基とをそれぞれ１個有する化合物が好ましい。 (Unsaturated hydroxy compound (A3))
The unsaturated hydroxy compound (A3) is a compound having a curable functional group and a hydroxyl group, and two or more curable functional groups may be present in one molecule, and two or more hydroxyl groups are present in one molecule. It may be. In order to produce an unsaturated urethane oligomer (A) having an average of 2 to 4 curable functional groups per molecule, a compound having one curable functional group and one hydroxyl group per molecule is preferred.
　不飽和ヒドロキシ化合物（Ａ３）としては、炭素数が１～１０のヒドロキシアルキルを有するヒドロキシアルキル（メタ）アクリレートが好ましく、炭素数が１～５のヒドロキシアルキルを有するヒドロキシアルキル（メタ）アクリレートがより好ましい。反応性の高い不飽和ウレタンオリゴマー（Ａ）を得るためには、硬化性官能基はアクリロイルオキシ基であることが好ましい。したがって、不飽和ヒドロキシ化合物（Ａ３）としては、炭素数が１～５のヒドロキシアルキルを有するヒドロキシアルキルアクリレートがさらに好ましい。 The unsaturated hydroxy compound (A3) is preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 10 carbon atoms, more preferably a hydroxyalkyl (meth) acrylate having a hydroxyalkyl having 1 to 5 carbon atoms. . In order to obtain a highly reactive unsaturated urethane oligomer (A), the curable functional group is preferably an acryloyloxy group. Therefore, the unsaturated hydroxy compound (A3) is more preferably a hydroxyalkyl acrylate having a hydroxyalkyl having 1 to 5 carbon atoms.
　不飽和ヒドロキシ化合物（Ａ３）の具体例としては、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレート、３－ヒドロキシプロピル（メタ）アクリレート、２－ヒドロキシブチル（メタ）アクリレート、４－ヒドロキシブチル（メタ）アクリレート、ペンタンジオールモノ（メタ）アクリレート、ヘキサンジオールモノ（メタ）アクリレート等が挙げられ、２－ヒドロキシエチル（メタ）アクリレート、２－ヒドロキシプロピル（メタ）アクリレートが好ましく、２－ヒドロキシエチルアクリレート、２－ヒドロキシプロピルアクリレートが特に好ましい。不飽和ヒドロキシ化合物（Ａ３）は、１種を単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the unsaturated hydroxy compound (A3) include 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 3-hydroxypropyl (meth) acrylate, 2-hydroxybutyl (meth) acrylate, 4 -Hydroxybutyl (meth) acrylate, pentanediol mono (meth) acrylate, hexanediol mono (meth) acrylate, and the like. 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate are preferred, Hydroxyethyl acrylate and 2-hydroxypropyl acrylate are particularly preferred. An unsaturated hydroxy compound (A3) may be used individually by 1 type, and may use 2 or more types together.
＜硬化性樹脂組成物＞
　本発明の硬化性樹脂組成物は、不飽和ウレタンオリゴマー（Ａ）を含む組成物であり、後述する、一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物として好適のものである。 <Curable resin composition>
The curable resin composition of the present invention is a composition containing an unsaturated urethane oligomer (A). The curable resin composition sandwiched between a pair of transparent substrates, which will be described later, is cured to form a transparent laminate. It is suitable as a curable resin composition used in the production method.
（その他の成分）
　不飽和ウレタンオリゴマー（Ａ）を含む硬化性樹脂組成物は、接着剤、コーティング剤、その他の用途に用いることができる。硬化性樹脂組成物には、用途に応じて種々の添加剤を添加できる。硬化性樹脂組成物を硬化させるための硬化剤の配合は通常必須であり、硬化剤としてはラジカル発生剤や光重合開始剤が好ましい。熱によりラジカルを発生する硬化剤が配合された硬化性樹脂組成物は熱硬化型となり、光重合開始剤が配合された硬化性樹脂組成物は光硬化型となる。 (Other ingredients)
The curable resin composition containing the unsaturated urethane oligomer (A) can be used for adhesives, coating agents, and other applications. Various additives can be added to the curable resin composition depending on the application. It is usually essential to add a curing agent for curing the curable resin composition, and a radical generator or a photopolymerization initiator is preferable as the curing agent. A curable resin composition containing a curing agent that generates radicals by heat is a thermosetting type, and a curable resin composition containing a photopolymerization initiator is a photocurable type.
　不飽和ウレタンオリゴマー（Ａ）を含む硬化性樹脂組成物には、硬化物の物性調整のために後述する単量体（Ｂ）、他の単量体（Ｆ）等の単量体が配合されることが好ましい。単量体としては、硬化性官能基の数が１～６である化合物が好ましく、硬化性官能基の数が１～２である化合物がより好ましい。硬質の硬化物を得る点では、硬化性官能基の数が３～６である化合物が好ましい。また、硬化性樹脂組成物の塗布性を高める点から、単量体としては、低粘度の化合物が好ましい。粘度の低い単量体は反応性希釈剤と呼ばれることもある。さらに、後述の他の不飽和オリゴマー（Ｅ）等の上記単量体以外の硬化性化合物を配合してもよい。 In the curable resin composition containing the unsaturated urethane oligomer (A), monomers such as a monomer (B) and other monomers (F) described later are blended for adjusting the physical properties of the cured product. It is preferable. As the monomer, a compound having 1 to 6 curable functional groups is preferable, and a compound having 1 to 2 curable functional groups is more preferable. From the viewpoint of obtaining a hard cured product, a compound having 3 to 6 curable functional groups is preferred. Moreover, a low viscosity compound is preferable as a monomer from the point which improves the applicability | paintability of curable resin composition. Monomers with low viscosity are sometimes referred to as reactive diluents. Furthermore, you may mix | blend curable compounds other than the said monomers, such as other below-mentioned unsaturated oligomer (E).
　硬化性樹脂組成物には反応に関与しない各種添加剤を配合してもよい。該添加剤としては、たとえば、後述の添加剤（Ｇ）等が挙げられる。また、塗布性を高めるために、硬化性樹脂組成物の構成成分以外の成分として溶剤を用いてもよい。溶剤を用いて硬化性樹脂組成物を塗布し、その後溶剤を除いて硬化性樹脂組成物を硬化させる。ただし、後述の透明積層体の製造に好適な硬化性樹脂組成物としては、揮発性成分を有することは好ましくないため、溶剤は用いない。 Various additives that do not participate in the reaction may be added to the curable resin composition. As this additive, the below-mentioned additive (G) etc. are mentioned, for example. Moreover, in order to improve applicability | paintability, you may use a solvent as components other than the structural component of curable resin composition. The curable resin composition is applied using a solvent, and then the curable resin composition is cured by removing the solvent. However, since it is not preferable to have a volatile component as a curable resin composition suitable for the production of a transparent laminate described later, no solvent is used.
（透明積層体の製造に好適な硬化性樹脂組成物）
　本発明の、一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物は、不飽和ウレタンオリゴマー（Ａ）を必須成分として含み、単量体（Ｂ）、単量体（Ｃ）光重合開始剤（Ｄ）、および／または他の不飽和オリゴマー（Ｅ）をさらに含むことが好ましく、必要に応じて他の単量体（Ｆ）、添加剤（Ｇ）等をさらに含んでいてもよい。 (Curable resin composition suitable for production of transparent laminate)
The curable resin composition used in the method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates according to the present invention comprises an unsaturated urethane oligomer (A) as an essential component. It is preferable that the monomer (B), the monomer (C), the photopolymerization initiator (D), and / or other unsaturated oligomers (E) are further contained, and if necessary, other monomers The body (F), additive (G), etc. may further be included.
　不飽和ウレタンオリゴマー（Ａ）は、硬化性樹脂組成物（１００質量％）中のリン含有量が０．１～５質量％になるように添加されることが好ましく、０．１～３質量％になるように添加されることがより好ましい。リン含有量が０．１質量％以上であれば、硬化性樹脂組成物を硬化して得られる硬化物が難燃性を発現できる。リン含有量が５質量％以下であれば、硬化物が硬く脆くならず、一対の透明基板間に挟持された硬化性樹脂組成物を硬化させた透明積層体の耐衝撃性が充分になる。 The unsaturated urethane oligomer (A) is preferably added so that the phosphorus content in the curable resin composition (100% by mass) is 0.1 to 5% by mass, and 0.1 to 3% by mass. It is more preferable to add so that it becomes. If phosphorus content is 0.1 mass% or more, the hardened | cured material obtained by hardening | curing curable resin composition can express a flame retardance. When the phosphorus content is 5% by mass or less, the cured product is not hard and brittle, and the impact resistance of the transparent laminate obtained by curing the curable resin composition sandwiched between the pair of transparent substrates is sufficient.
　不飽和ウレタンオリゴマー（Ａ）は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部のうち、１０～１００質量部が好ましく、４０～６０質量部がより好ましい。不飽和ウレタンオリゴマー（Ａ）が１０質量部以上であれば、硬化物の難燃性が良好となる。
　単量体（Ｂ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部のうち、２５～６５質量部が好ましく、３５～５０質量部がより好ましい。単量体（Ｂ）が６５質量部以下であると、不飽和ウレタンオリゴマー（Ａ）との相溶性が良好で、硬化性組成物を硬化して得られる硬化物が充分な透明性を有する。 The unsaturated urethane oligomer (A) is preferably 10 to 100 parts by mass, more preferably 40 to 60 parts by mass, out of a total of 100 parts by mass of the components (A) to (C), (E) and (F). If unsaturated urethane oligomer (A) is 10 mass parts or more, the flame retardance of hardened | cured material will become favorable.
When the monomer (B) is included, 25 to 65 parts by mass is preferable, and 35 to 50 parts by mass is preferable among 100 parts by mass in total of the components (A) to (C), (E) and (F). More preferred. When the monomer (B) is 65 parts by mass or less, the compatibility with the unsaturated urethane oligomer (A) is good, and the cured product obtained by curing the curable composition has sufficient transparency.
　単量体（Ｃ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部のうち、３～５０質量部が好ましく、５～２５質量部がより好ましい。単量体（Ｃ）の割合が３質量部以上であれば、硬化物の柔軟性が向上し、硬化性樹脂組成物の粘度も下げることができ、工業的に有用である。
　光重合開始剤（Ｄ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部に対して、０．０１～１０質量部が好ましく、０．１～２．５質量部がより好ましい。 When the monomer (C) is included, 3 to 50 parts by mass is preferable, and 5 to 25 parts by mass is preferable among 100 parts by mass in total of the components (A) to (C), (E) and (F). More preferred. If the ratio of a monomer (C) is 3 mass parts or more, the softness | flexibility of hardened | cured material can improve and the viscosity of curable resin composition can also be lowered | hung, and it is industrially useful.
When the photopolymerization initiator (D) is included, the amount is preferably 0.01 to 10 parts by mass with respect to 100 parts by mass in total of the components (A) to (C), (E) and (F). 1 to 2.5 parts by mass is more preferable.
　他のオリゴマー（Ｅ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部のうち、３～５５質量部が好ましく、３０～５０質量部がより好ましい。他のオリゴマー（Ｅ）の割合が３質量部以上であれば、硬化物の柔軟性が向上し、硬化性樹脂組成物の粘度も下げることができ、工業的に有用である。
　他の単量体（Ｆ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部のうち、５０質量部以下が好ましく、４０質量部以下がより好ましい。
　添加剤（Ｇ）を含ませる場合は、（Ａ）～（Ｃ）、（Ｅ）および（Ｆ）成分の合計１００質量部に対して、５質量部以下が好ましく、３質量部以下がより好ましい。 When other oligomer (E) is included, 3 to 55 parts by mass is preferable, and 30 to 50 parts by mass is preferable among 100 parts by mass of the total of components (A) to (C), (E) and (F). More preferred. When the ratio of the other oligomer (E) is 3 parts by mass or more, the flexibility of the cured product is improved and the viscosity of the curable resin composition can be lowered, which is industrially useful.
When other monomer (F) is included, 50 parts by mass or less is preferable and 100 parts by mass or less is preferable among the total 100 parts by mass of components (A) to (C), (E) and (F). More preferred.
When the additive (G) is included, it is preferably 5 parts by mass or less, more preferably 3 parts by mass or less with respect to 100 parts by mass in total of the components (A) to (C), (E) and (F). .
（単量体（Ｂ））
　単量体（Ｂ）は、ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ２で表される化合物（ただし、Ｒは水素原子またはメチル基であり、Ｒ２は水酸基数が１～２であり、炭素数が３～４のヒドロキシアルキル基である。）である。単量体（Ｂ）は、硬化性樹脂組成物の硬化物の親水性を高めて硬化物と透明基材（ガラス板）の表面との親和性を向上させる成分として有効であり、単量体（Ｂ）の用いることにより硬化物と透明基板との密着性が向上する。 (Monomer (B))
The monomer (B) is a compound represented by CH 2 ═C (R) C (O) O—R 2 (where R is a hydrogen atom or a methyl group, and R 2 has 1 to 2 hydroxyl groups) And a hydroxyalkyl group having 3 to 4 carbon atoms. The monomer (B) is effective as a component that increases the hydrophilicity of the cured product of the curable resin composition and improves the affinity between the cured product and the surface of the transparent substrate (glass plate). By using (B), the adhesion between the cured product and the transparent substrate is improved.
　単量体（Ｂ）はヒドロキシアルキル基またはジヒドロキシアルキル基を有する（メタ）アクリレートであり、不飽和ウレタンオリゴマー（Ａ）との反応を均一に進めるためにはメタクリレートであることが好ましい。すなわち、不飽和ウレタンオリゴマー（Ａ）の硬化性官能基はたとえアクリロイルオキシ基であっても反応性が低く、単量体（Ｂ）の硬化性官能基がアクリロイルオキシ基であると両硬化性官能基の反応性の差が大きくなり、均一な硬化が得られないおそれがある。よって、不飽和ウレタンオリゴマー（Ａ）の硬化性官能基がアクリロイルオキシ基であり、単量体（Ｂ）の硬化性官能基がメタクリロイルオキシ基である組み合わせが好ましい。単量体（Ｂ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 The monomer (B) is a (meth) acrylate having a hydroxyalkyl group or a dihydroxyalkyl group, and is preferably a methacrylate in order to proceed the reaction with the unsaturated urethane oligomer (A) uniformly. That is, even if the curable functional group of the unsaturated urethane oligomer (A) is an acryloyloxy group, the reactivity is low, and if the curable functional group of the monomer (B) is an acryloyloxy group, both curable functional groups There is a possibility that a difference in reactivity between groups becomes large and uniform curing cannot be obtained. Therefore, a combination in which the curable functional group of the unsaturated urethane oligomer (A) is an acryloyloxy group and the curable functional group of the monomer (B) is a methacryloyloxy group is preferable. A monomer (B) may be used individually by 1 type, and may use 2 or more types together.
　単量体（Ｂ）の水酸基数が２以下であると、硬化物が脆くなりにくい。したがって、Ｒ２の水酸基数は１～２であり、１であることがより好ましい。
　単量体（Ｂ）のＲ２の炭素数は３～４である。Ｒ２の炭素数が３以上では、長鎖構造の不飽和ウレタンオリゴマー（Ａ）との相溶性が良好で、硬化性組成物を硬化して得られる硬化物が充分な透明性を有する。Ｒ２の炭素数が４以下では、水酸基密度が高くなり、充分な密着性が得られる。 When the number of hydroxyl groups of the monomer (B) is 2 or less, the cured product is hardly brittle. Accordingly, the number of hydroxyl groups in R 2 is 1 to 2, and more preferably 1.
The number of carbon atoms in R 2 of the monomer (B) is 3-4. When R 2 has 3 or more carbon atoms, the compatibility with the unsaturated urethane oligomer (A) having a long chain structure is good, and a cured product obtained by curing the curable composition has sufficient transparency. When the carbon number of R 2 is 4 or less, the hydroxyl group density becomes high and sufficient adhesion can be obtained.
　単量体（Ｂ）としては、２－ヒドロキシプロピルメタクリレート、２－ヒドロキシブチルメタクリレート、４－ヒドロキシブチルメタクリレート等が挙げられ、２－ヒドロキシブチルメタクリレートが好ましい。 Examples of the monomer (B) include 2-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, 4-hydroxybutyl methacrylate and the like, and 2-hydroxybutyl methacrylate is preferable.
（単量体（Ｃ））
　単量体（Ｃ）は、ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ３で表される化合物（ただし、Ｒは水素原子またはメチル基であり、Ｒ３は炭素数が８～２２のアルキル基である。）である。単量体（Ｂ）と同様の理由により単量体（Ｃ）はメタクリレートであることが好ましいが、単量体（Ｃ）は単量体（Ｂ）よりも高分子量であることから、場合によりアクリレートであってもよい。単量体（Ｃ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 (Monomer (C))
The monomer (C) is a compound represented by CH 2 ═C (R) C (O) O—R 3 (wherein R is a hydrogen atom or a methyl group, and R 3 has 8 to 22 carbon atoms) It is an alkyl group of For the same reason as the monomer (B), the monomer (C) is preferably methacrylate, but the monomer (C) has a higher molecular weight than the monomer (B), so it may be An acrylate may also be used. A monomer (C) may be used individually by 1 type, and may use 2 or more types together.
　硬化性樹脂組成物が単量体（Ｃ）を含むことにより、硬化物の弾性率が低下し、耐引き裂き性が向上しやすい。また、アルキル基の炭素数が８以上であれば、揮発性が少なく、また硬化物のガラス転移温度を低下させることができる。アルキル基の炭素数が２２以下であれば、原料のアルコール成分を天然物経由で容易に入手でき、より工業的である。 When the curable resin composition contains the monomer (C), the elastic modulus of the cured product is lowered, and the tear resistance is easily improved. Moreover, if carbon number of an alkyl group is 8 or more, there is little volatility and the glass transition temperature of hardened | cured material can be reduced. When the carbon number of the alkyl group is 22 or less, the alcohol component of the raw material can be easily obtained via a natural product and is more industrial.
　単量体（Ｃ）としては、ｎ－ドデシルメタクリレート、ｎ－オクタデシルメタクリレート、ｎ－ベヘニルメタクリレート等が挙げられ、ｎ－ドデシルメタクリレート、ｎ－オクタデシルメタクリレートが特に好ましい。 Examples of the monomer (C) include n-dodecyl methacrylate, n-octadecyl methacrylate, n-behenyl methacrylate and the like, and n-dodecyl methacrylate and n-octadecyl methacrylate are particularly preferable.
（光重合開始剤（Ｄ））
　本発明の硬化性樹脂組成物が光重合開始剤（Ｄ）を含むことにより、光硬化性樹脂組成物となる。
　光重合開始剤（Ｄ）としては、可視光線または紫外線（波長３００～４００ｎｍ）の照射により励起され、活性化して硬化反応を促進するものが好ましく、ベンゾインエーテル系光重合開始剤、α－ヒドロキシアルキルフェノン系光重合開始剤、アシルフォスフィンオキシド系光重合開始剤等が挙げられる。 (Photopolymerization initiator (D))
When the curable resin composition of this invention contains a photoinitiator (D), it becomes a photocurable resin composition.
As the photopolymerization initiator (D), those which are excited by irradiation with visible light or ultraviolet light (wavelength 300 to 400 nm) and are activated to accelerate the curing reaction are preferable. A benzoin ether photopolymerization initiator, α-hydroxyalkyl Examples thereof include a phenone photopolymerization initiator and an acyl phosphine oxide photopolymerization initiator.
　光重合開始剤（Ｄ）の具体例としては、ベンゾフェノン、４－クロロベンゾフェノン、４、４’－ジメトキシベンゾフェノン、４、４’－ジアミノベンゾフェノン、アセトフェノン、３－メチルアセトフェノン、ベンゾイル、ベンゾインイソブチルエーテル、ベンゾインイソプロピルエーテル、ベンゾインエチルエーテル、アントラキノン、１－ヒドロキシシクロヘキシルフェニルケトン、２－ヒドロキシ－２－メチル－１－フェニルプロパン－１－オン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキシド等が挙げられ、１－ヒドロキシシクロヘキシルフェニルケトン、１－［４－（２－ヒドロキシエトキシ）－フェニル］－２－ヒドロキシ－２－メチル－１－プロパン－１－オン、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキシド等が好ましく、微量の添加においても充分に硬化性樹脂組成物を硬化できる点から、ビス（２，４，６－トリメチルベンゾイル）－フェニルフォスフィンオキシド等のアシルフォスフィンオキシド系光重合開始剤が特に好ましい。光重合開始剤（Ｄ）は、１種を単独で用いてもよく、２種以上を併用してもよい。 Specific examples of the photopolymerization initiator (D) include benzophenone, 4-chlorobenzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, acetophenone, 3-methylacetophenone, benzoyl, benzoin isobutyl ether, benzoin Isopropyl ether, benzoin ethyl ether, anthraquinone, 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1- [4- (2-hydroxyethoxy) -phenyl] -2- Hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, and the like, such as 1-hydroxycyclohexyl phenyl ketone, 1- [4- (2- Hydro Ethoxy) -phenyl] -2-hydroxy-2-methyl-1-propan-1-one, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide, etc. are preferred, and they can be cured sufficiently even with a small amount of addition. An acyl phosphine oxide-based photopolymerization initiator such as bis (2,4,6-trimethylbenzoyl) -phenyl phosphine oxide is particularly preferable from the viewpoint of curing the conductive resin composition. A photoinitiator (D) may be used individually by 1 type, and may use 2 or more types together.
（他の不飽和オリゴマー（Ｅ））
　本発明の硬化性樹脂組成物は、組成物の粘度や硬化物の物性を調整する目的で、不飽和ウレタンオリゴマー（Ａ）以外の他の不飽和オリゴマー（Ｅ）を少量含んでいてもよい。
　他の不飽和オリゴマー（Ｅ）としては、リン原子を含有しないポリオールを用いて得られるウレタン（メタ）アクリレートオリゴマー、ポリオキシアルキレンポリオールのポリ（メタ）アクリレート、ポリエステルポリオールのポリ（メタ）アクリレート等が挙げられる。 (Other unsaturated oligomers (E))
The curable resin composition of the present invention may contain a small amount of an unsaturated oligomer (E) other than the unsaturated urethane oligomer (A) for the purpose of adjusting the viscosity of the composition and the physical properties of the cured product.
Other unsaturated oligomers (E) include urethane (meth) acrylate oligomers obtained using polyols that do not contain phosphorus atoms, poly (meth) acrylates of polyoxyalkylene polyols, poly (meth) acrylates of polyester polyols, and the like. Can be mentioned.
（他の単量体（Ｆ））
　本発明の硬化性樹脂組成物は、得られる硬化物の物性を調整する目的で、単量体（Ｂ）および単量体（Ｃ）以外の他の単量体（Ｆ）（（メタ）アクリレート類等）を少量含んでいてもよい。他の単量体（Ｆ）としては、多価アルコールのポリ（メタ）アクリレート等が挙げられる。 (Other monomer (F))
The curable resin composition of the present invention is a monomer (F) ((meth) acrylate other than the monomer (B) and the monomer (C) for the purpose of adjusting the physical properties of the resulting cured product. Etc.) may be included in a small amount. Examples of the other monomer (F) include poly (meth) acrylate of polyhydric alcohol.
　ただし、後述の減圧積層方法で透明積層体を製造する場合は、硬化性樹脂組成物が低沸点の化合物を含むことは好ましくない。周辺をシールした一対の透明基板の間に液状の硬化性樹脂組成物を注入して硬化させる方法では、たとえ透明基板の間を減圧にして注入する場合であっても、注入時に減圧にさらされる硬化性樹脂組成物の表面の面積は狭く、また、減圧度もさほど高くする必要がないことから、硬化性樹脂組成物が比較的低沸点の化合物を含んでいてもその揮発が問題となることは少ない。一方、減圧積層方法では、透明基板の周縁部を除くほぼ全面に硬化性樹脂組成物が広がった状態で減圧にさらされることから、硬化性樹脂組成物が低沸点の化合物を含んでいるとその揮発による消失が激しく、硬化性樹脂組成物の組成が大きく変化するおそれがある。加えて、揮発性化合物の揮発により必要な減圧度の減圧雰囲気を維持することが困難となる。 However, when a transparent laminate is produced by the below-described reduced pressure lamination method, it is not preferable that the curable resin composition contains a low boiling point compound. In the method of injecting and curing a liquid curable resin composition between a pair of transparent substrates sealed at the periphery, even when injecting with a reduced pressure between the transparent substrates, it is exposed to a reduced pressure at the time of injection. Since the surface area of the curable resin composition is narrow and the degree of vacuum need not be so high, volatilization is a problem even if the curable resin composition contains a compound having a relatively low boiling point. There are few. On the other hand, in the reduced pressure laminating method, the curable resin composition is exposed to reduced pressure in a state where the curable resin composition spreads over almost the entire surface excluding the peripheral portion of the transparent substrate. The disappearance due to volatilization is severe, and the composition of the curable resin composition may change greatly. In addition, it becomes difficult to maintain a reduced pressure atmosphere at a required reduced pressure level due to volatilization of volatile compounds.
　硬化性樹脂組成物中の低沸点となりやすい成分は主に単量体である。単量体（Ｂ）は、ヒドロキシアルキル（メタ）アクリレートであり、その沸点は充分に高い。また、単量体（Ｃ）は、アルキル（メタ）アクリレートであってもアルキル基の炭素数が大きいことより高い沸点を有する。アルキル基の炭素数の低いアルキル（メタ）アクリレートは低沸点であることが多く、このような低沸点のアルキル（メタ）アクリレートを他の単量体（Ｆ）として含む硬化性樹脂組成物は、減圧積層方法で透明積層体を製造するための硬化性樹脂組成物として用いることができない。減圧積層方法に用いることができる硬化性樹脂組成物は、常圧の沸点が１５０℃以下、好ましくは２００℃以下の単量体を含まないことが好ましい。 Components that tend to have a low boiling point in the curable resin composition are mainly monomers. The monomer (B) is a hydroxyalkyl (meth) acrylate and has a sufficiently high boiling point. Further, the monomer (C) has a higher boiling point than the alkyl group having a large number of carbon atoms, even if it is an alkyl (meth) acrylate. Alkyl (meth) acrylates having a low carbon number of the alkyl group often have a low boiling point, and the curable resin composition containing such a low boiling point alkyl (meth) acrylate as another monomer (F) is: It cannot be used as a curable resin composition for producing a transparent laminate by a reduced pressure lamination method. The curable resin composition that can be used in the reduced pressure lamination method preferably does not contain a monomer having a normal pressure boiling point of 150 ° C. or lower, preferably 200 ° C. or lower.
（添加剤（Ｇ））
　添加剤（Ｇ）としては、紫外線吸収剤（ベンゾトリアゾール系、ヒドロキシフェニルトリアジン系等。）、光安定剤（ヒンダードアミン系等。）、顔料、染料、金属酸化物微粒子、フィラー等が挙げられる。 (Additive (G))
Examples of the additive (G) include ultraviolet absorbers (benzotriazoles, hydroxyphenyltriazines, etc.), light stabilizers (hindered amines, etc.), pigments, dyes, metal oxide fine particles, fillers, and the like.
（硬化性樹脂組成物の粘度）
　本発明の、透明積層体を製造する方法に用いられる硬化性樹脂組成物の粘度は、他の用途に使用できる前記本発明硬化性樹脂組成物の粘度も同様に、４０℃での粘度Ｖ４０で５０Ｐａ・ｓ以下であることが好ましい。また、２５℃での粘度Ｖ２５は０．０５Ｐａ・ｓ以上であることが好ましい。
　粘度測定は、Ｅ型粘度計（東機産業社製、ＲＥ－８５Ｕ）を用いて測定する。ただし、組成物の粘度が１００Ｐａ・ｓ以下の場合は、ロータとして１°３４'×Ｒ２４を用い、それ以上の粘度の場合は、ロータとして３°×Ｒ９．7を用いる。 (Viscosity of curable resin composition)
Of the present invention, the viscosity of the curable resin composition used in the method for producing a transparent laminate, likewise the viscosity of the present invention curable resin composition which can be used in other applications, the viscosity V 40 at 40 ° C. It is preferably 50 Pa · s or less. The viscosity V 25 at 25 ° C. is preferably 0.05 Pa · s or more.
The viscosity is measured using an E-type viscometer (manufactured by Toki Sangyo Co., Ltd., RE-85U). However, when the viscosity of the composition is 100 Pa · s or less, 1 ° 34 ′ × R24 is used as the rotor, and when the viscosity is higher than that, 3 ° × R9.7 is used as the rotor.
　粘度Ｖ４０が５０Ｐａ・ｓ以下であると流動性が良好で、後述する減圧積層方法に用いる場合に硬化性樹脂組成物中に消失しにくい気泡が生成しにくい。ただし、硬化性樹脂組成物を、溶剤を用いることができる用途に用いる場合は、溶剤を配合して流動性を高めて塗布等を行い、その後溶剤を除いて得られる硬化性樹脂組成物を硬化させることができる。硬化性樹脂組成物のＶ２５を０．０５Ｐａ・ｓ以上にすると、硬化物の物性が良好になる。 When the viscosity V 40 is 50 Pa · s or less, the fluidity is good, and when used in the reduced pressure laminating method described later, bubbles that do not easily disappear in the curable resin composition are hardly generated. However, when the curable resin composition is used for an application in which a solvent can be used, the solvent is added to increase fluidity to perform application, etc., and then the curable resin composition obtained by removing the solvent is cured. Can be made. When V 25 of the curable resin composition is 0.05 Pa · s or more, the physical properties of the cured product are improved.
　以上説明した本発明の、透明積層体を製造する方法に用いられる硬化性樹脂組成物にあっては、上述した特定のポリオール成分（Ａ１）を用いて得られた特定の不飽和ウレタンオリゴマー（Ａ）を含んでいるため、該組成物を硬化した場合には、透明性に優れ、かつ難燃性に優れる硬化物となる。 In the curable resin composition used in the method for producing the transparent laminate of the present invention described above, the specific unsaturated urethane oligomer (A) obtained by using the specific polyol component (A1) described above. Therefore, when the composition is cured, a cured product having excellent transparency and flame retardancy is obtained.
　本発明の硬化性樹脂組成物は、後述の透明積層体を製造するための硬化性樹脂組成物として使用することが好ましい。しかし、この用途に限られず、硬化性樹脂として、特に光硬化性樹脂として他の用途に使用することもできる。他の用途としては、後述の透明積層体と同様の構成を有し、一方の透明基板が不透明基板または透過光の透過率が低い透明基板である積層体を製造するための硬化性樹脂組成物である。そのような積層体としては、たとえば、太陽電池モジュールがある。このような積層体は、少なくとも片側の基板が透明であることで光硬化性樹脂組成物の硬化に必要な光の入射が可能である。両面の基板が不透明な場合には、熱硬化性樹脂組成物を用い熱硬化させることもできるが、不透明基板が可視光に対して不透明であっても、たとえば光硬化に必要な紫外線に対して透明であれば、両面が不透明基板であっても光硬化性樹脂組成物を用いることができる。 The curable resin composition of the present invention is preferably used as a curable resin composition for producing a transparent laminate described later. However, the present invention is not limited to this application, and can be used for other applications as a curable resin, particularly as a photocurable resin. As other uses, a curable resin composition for producing a laminate having the same structure as the transparent laminate described later, wherein one transparent substrate is an opaque substrate or a transparent substrate having low transmittance of transmitted light. It is. An example of such a laminate is a solar cell module. In such a laminate, at least one substrate is transparent so that light necessary for curing the photocurable resin composition can be incident thereon. When the substrates on both sides are opaque, the thermosetting resin composition can be used for thermosetting, but even if the opaque substrate is opaque to visible light, for example against ultraviolet rays necessary for photocuring. If it is transparent, a photocurable resin composition can be used even if both surfaces are opaque substrates.
　光透過率が低い透明基板として、薄膜太陽電池が形成されたガラス基板を用い、対向のガラス基板との間に本発明の硬化性樹脂組成物の硬化物からなる層を形成して太陽電池モジュールを提供することができる。本発明の硬化性樹脂組成物の硬化物からなる接合層により、太陽電池モジュールに難燃性能を付与することができ、建造物に設置する際に安全性を高めることができる。薄膜太陽電池としては、薄膜シリコンや化合物半導体（銅－インジウム－ガリウム－セレン等）による発電層を用いることができる。両面のガラス基板に薄膜シリコンによる発電層を設けたり、薄膜シリコン基板と化合物半導体の薄膜を形成したガラス基板を組み合わせて積層させたりすることもできる。なお、太陽電池モジュールの場合、ガラス基板等の両面の基板はいずれも透明であってもよい。 As a transparent substrate with low light transmittance, a glass substrate on which a thin film solar cell is formed is used, and a layer made of a cured product of the curable resin composition of the present invention is formed between the glass substrate and a solar cell module. Can be provided. By the joining layer which consists of hardened | cured material of the curable resin composition of this invention, a flame retardance performance can be provided to a solar cell module, and safety | security can be improved when installing in a building. As the thin film solar cell, a power generation layer made of thin film silicon or a compound semiconductor (such as copper-indium-gallium-selenium) can be used. A power generation layer made of thin film silicon can be provided on both glass substrates, or a thin film silicon substrate and a glass substrate on which a compound semiconductor thin film is formed can be combined and laminated. In the case of a solar cell module, both substrates such as a glass substrate may be transparent.
　さらに、一対のガラス基板の間に、単結晶シリコンや微結晶シリコンからなる複数の太陽電池基板を配置して、本発明の硬化性樹脂組成物の硬化物によって、太陽電池基板をガラス基板間に封入することもできる。ガラス基板の片方を防水樹脂シートとしてもよい。このような太陽電池モジュールは難燃性を有し、建造物に設置する際に安全性が高まる。また、封入される太陽電池基板の一部に不良が発生して過度の電流が流れるなどして発熱したとしても、本発明の硬化性樹脂組成物の硬化物をその封入樹脂として用いることで封入樹脂が難燃性を有するため安全性を高めることができる。 Furthermore, a plurality of solar cell substrates made of single crystal silicon or microcrystalline silicon are arranged between a pair of glass substrates, and the solar cell substrate is interposed between the glass substrates by a cured product of the curable resin composition of the present invention. It can also be enclosed. One side of the glass substrate may be a waterproof resin sheet. Such a solar cell module has flame retardancy, and safety is improved when it is installed in a building. In addition, even if a part of the solar cell substrate to be encapsulated is defective and excessive current flows to generate heat, it is encapsulated by using the cured product of the curable resin composition of the present invention as the encapsulating resin. Since the resin has flame retardancy, safety can be improved.
＜透明積層体＞
　本発明の透明積層体は、一対の透明基板と、該透明基板の間に挟まれた硬化樹脂層とを有する。なお、該透明積層体や該透明基板は、可視光線に対して透明であることを意味する。 <Transparent laminate>
The transparent laminate of the present invention has a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates. In addition, this transparent laminated body and this transparent substrate mean that it is transparent with respect to visible light.
　透明基板としては、ガラス板または樹脂板が挙げられる。ガラス板を用いれば、合わせガラスが得られる。樹脂板としてポリカーボネート板を用いれば、耐衝撃性が高く軽量な透明パネルが得られる。また、ガラス板と樹脂板とを組み合わせて用いてもよい。
　透明基板の大きさは、特に限定されないが、３００ｍｍ以上、より好ましくは６００ｍｍ以上の辺を少なくとも１つ有する透明基板であれば、建築用や車両用の開口部に設置する透明部材として広く利用できる。通常の用途においては、４ｍ２以下の大きさが適当である。 Examples of the transparent substrate include a glass plate or a resin plate. If a glass plate is used, a laminated glass is obtained. If a polycarbonate plate is used as the resin plate, a lightweight transparent panel having high impact resistance can be obtained. Further, a glass plate and a resin plate may be used in combination.
The size of the transparent substrate is not particularly limited, but can be widely used as a transparent member to be installed in an opening for a building or a vehicle if it is a transparent substrate having at least one side of 300 mm or more, more preferably 600 mm or more. . In normal applications, a size of 4 m 2 or less is appropriate.
　透明積層体に含まれる硬化樹脂の層は、本発明の硬化性樹脂組成物の硬化物からなる層である。
　硬化樹脂の層の厚さは、０．２～４．０ｍｍが好ましい。硬化樹脂の層の厚さが０．２ｍｍ以上であれば、透明積層体の機械的強度が良好となる。硬化樹脂の層の厚さが４．０ｍｍ以下であれば、透明積層体の透明性に優れ、窓ガラスとして用いることができる。 The layer of the cured resin contained in the transparent laminate is a layer made of a cured product of the curable resin composition of the present invention.
The thickness of the cured resin layer is preferably 0.2 to 4.0 mm. When the thickness of the cured resin layer is 0.2 mm or more, the mechanical strength of the transparent laminate is good. When the thickness of the cured resin layer is 4.0 mm or less, the transparent laminate is excellent in transparency and can be used as a window glass.
　以上説明した本発明の透明積層体にあっては、透明基板の間に挟まれた硬化樹脂の層が本発明の硬化性樹脂組成物の硬化物からなるため、透明性に優れ、かつ難燃性に優れる。 In the transparent laminate of the present invention described above, the cured resin layer sandwiched between the transparent substrates is made of a cured product of the curable resin composition of the present invention, and thus has excellent transparency and flame retardancy. Excellent in properties.
＜透明積層体の製造方法＞
　本発明の透明積層体は、公知の製造方法（たとえば、一対の透明基板の間に硬化性樹脂組成物を挟持させ、該硬化性樹脂組成物を硬化させる方法等）によって製造でき、本発明の硬化性樹脂組成物を用いた減圧積層方法によって製造することが好ましい。減圧積層方法自体は、国際公開第２００８／０８１８３８号や国際公開第２００９／０１６９４３号に記載されている。 <Method for producing transparent laminate>
The transparent laminate of the present invention can be produced by a known production method (for example, a method of sandwiching a curable resin composition between a pair of transparent substrates and curing the curable resin composition). It is preferable to manufacture by a reduced pressure lamination method using a curable resin composition. The decompression lamination method itself is described in International Publication No. 2008/081838 and International Publication No. 2009/016943.
　減圧積層方法の特徴は、１枚の透明基板上に硬化性樹脂組成物の層を形成し、減圧雰囲気下で硬化性樹脂組成物の層の上にもう１枚の透明基板を重ねて２枚の透明基板の間に硬化性樹脂組成物を密閉し、その後、前記減圧雰囲気よりも高い圧力雰囲気（通常は大気圧雰囲気）に置いて硬化性樹脂組成物を硬化させることにある。このため、本発明の透明積層体の製造方法は、下記第１の工程と第２の工程とを必須とする。 The feature of the reduced pressure lamination method is that a curable resin composition layer is formed on one transparent substrate, and another transparent substrate is stacked on the curable resin composition layer in a reduced pressure atmosphere. The curable resin composition is hermetically sealed between the transparent substrates and then placed in a pressure atmosphere (usually an atmospheric pressure atmosphere) higher than the reduced-pressure atmosphere to cure the curable resin composition. For this reason, the manufacturing method of the transparent laminated body of this invention makes the following 1st process and 2nd process essential.
　第１の工程：減圧雰囲気中で、一対の透明基板間に硬化性樹脂組成物を内部に収容した密閉空間を形成して、一対の透明基板と該一対の透明基板間に密閉された前記硬化性樹脂組成物とを有する積層前駆体を製造する工程。
　第２の工程：前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる工程。 1st process: The said hardening which formed the sealed space which accommodated the curable resin composition inside between a pair of transparent substrates in a pressure-reduced atmosphere, and was sealed between a pair of transparent substrates and this pair of transparent substrates. The process of manufacturing the lamination | stacking precursor which has a conductive resin composition.
2nd process: The process of putting the said lamination | stacking precursor in the atmosphere whose pressure is higher than the said pressure reduction atmosphere, and hardening the said curable resin composition in the atmosphere.
　第１の工程における減圧雰囲気は、１ｋＰａ以下の圧力雰囲気が好ましく、１００Ｐａ以下の圧力雰囲気がより好ましい。また、減圧雰囲気の圧力があまりに低すぎると単量体等の硬化性樹脂組成物の揮発のおそれが生じることから、減圧雰囲気は１Ｐａ以上の圧力雰囲気が好ましく、１０Ｐａ以上の圧力雰囲気がより好ましい。
　第２の工程における、前記減圧雰囲気よりも圧力が高い雰囲気としては、５０ｋＰａ以上の圧力雰囲気が好ましく、１００ｋＰａ以上の圧力雰囲気がより好ましい。第２の工程における圧力雰囲気は、通常、大気圧雰囲気である。
　以下、前記減圧雰囲気よりも圧力が高い雰囲気が大気圧雰囲気である場合を例として該製造方法を説明する。 The reduced pressure atmosphere in the first step is preferably a pressure atmosphere of 1 kPa or less, and more preferably a pressure atmosphere of 100 Pa or less. Further, if the pressure in the reduced-pressure atmosphere is too low, the curable resin composition such as a monomer may be volatilized. Therefore, the reduced-pressure atmosphere is preferably a pressure atmosphere of 1 Pa or more, and more preferably a pressure atmosphere of 10 Pa or more.
The atmosphere having a higher pressure than the reduced-pressure atmosphere in the second step is preferably a pressure atmosphere of 50 kPa or more, and more preferably a pressure atmosphere of 100 kPa or more. The pressure atmosphere in the second step is usually an atmospheric pressure atmosphere.
Hereinafter, the production method will be described by taking as an example the case where the atmosphere having a higher pressure than the reduced pressure atmosphere is an atmospheric pressure atmosphere.
　第１の工程において、密閉空間内の硬化性樹脂組成物に気泡が残存しても硬化性樹脂組成物が硬化する前にその気泡は消失しやすく、気泡のない硬化樹脂の層が得られやすい。第１の工程で形成された積層前駆体を大気圧下に置くと、大気圧下の透明基板からの圧力により密閉空間内の硬化性樹脂組成物にも圧力がかかる。一方、硬化性樹脂組成物中の気泡内部は第１の工程の減圧雰囲気圧力にあることから、第２の工程では硬化性樹脂組成物にかかる圧力によりこの気泡の体積が縮小し、また気泡内の気体が硬化性樹脂組成物に溶解することにより、気泡が消失するに至る。気泡を消失させるために、硬化性樹脂組成物を硬化させる前に積層前駆体をしばらく大気圧下に保持することが好ましい。保持時間は５分以上が好ましいが、気泡がない場合や気泡が微小で速やかに消失する場合などでは保持時間はさらに短時間であってもよい。 In the first step, even if bubbles remain in the curable resin composition in the sealed space, the bubbles are likely to disappear before the curable resin composition is cured, and a cured resin layer having no bubbles is easily obtained. . When the laminated precursor formed in the first step is placed under atmospheric pressure, pressure is also applied to the curable resin composition in the sealed space due to the pressure from the transparent substrate under atmospheric pressure. On the other hand, since the inside of the bubbles in the curable resin composition is at the reduced-pressure atmospheric pressure in the first step, the volume of the bubbles is reduced by the pressure applied to the curable resin composition in the second step. When this gas dissolves in the curable resin composition, the bubbles disappear. In order to eliminate bubbles, it is preferable to hold the lamination precursor under atmospheric pressure for a while before the curable resin composition is cured. The holding time is preferably 5 minutes or more, but the holding time may be shorter when there are no bubbles or when the bubbles are very small and quickly disappear.
　第１の工程において、減圧雰囲気は密閉空間を形成する段階で必要とし、それ以前の段階では必要としない。たとえば、一方の透明基板の一方の面の周辺部全周に所定の厚さのシール材を設け、シール材に囲まれた領域内の透明基板表面に硬化性樹脂組成物を供給して硬化性樹脂組成物の層を形成する場合、これらの段階では大気圧雰囲気で行うことができる。密閉空間の形成は以下のように行うことが好ましい。 In the first process, the reduced pressure atmosphere is required at the stage of forming the sealed space, and is not required at the stage before that. For example, a sealing material having a predetermined thickness is provided around the periphery of one surface of one transparent substrate, and the curable resin composition is supplied to the surface of the transparent substrate in a region surrounded by the sealing material to be curable. When forming the layer of the resin composition, these steps can be performed in an atmospheric pressure atmosphere. The sealed space is preferably formed as follows.
　前記のようにして得られた硬化性樹脂組成物の層を有する透明基板と、他方の透明基板とを減圧チャンバーに入れ、所定の配置とする。すなわち、硬化性樹脂組成物の層を有する透明基板を、硬化性樹脂組成物の層を上にして水平な定盤上に乗せ、他方の透明基板を、上下しうるシリンダーの先に取り付けられた水平な定盤の下面に取り付け、硬化性樹脂組成物の層が他方の透明基板に接触させることなく、両透明基板を平行に位置させる。その後、減圧チャンバーを閉じて排気し、減圧チャンバー内を所定の減圧雰囲気とする。減圧チャンバー内が所定の減圧雰囲気となった後、シリンダーを作動させて両透明基板を硬化性樹脂組成物の層を介して重ね、両透明基板とシール材で囲まれた空間内に硬化性樹脂組成物を密閉し、積層前駆体を形成する。積層前駆体を形成した後、減圧チャンバー内を大気圧雰囲気の戻し、減圧チャンバーから積層前駆体を取り出す。 The transparent substrate having the layer of the curable resin composition obtained as described above and the other transparent substrate are put in a reduced pressure chamber and set in a predetermined arrangement. That is, a transparent substrate having a layer of a curable resin composition was placed on a horizontal surface plate with the layer of the curable resin composition facing up, and the other transparent substrate was attached to the tip of a cylinder that could be moved up and down. It attaches to the lower surface of a horizontal surface plate, and both transparent substrates are located in parallel, without making the layer of curable resin composition contact the other transparent substrate. Thereafter, the decompression chamber is closed and evacuated, and the inside of the decompression chamber is set to a predetermined decompressed atmosphere. After the inside of the decompression chamber becomes a predetermined decompression atmosphere, the cylinder is operated and both transparent substrates are overlapped via the layer of the curable resin composition, and the curable resin is placed in the space surrounded by the both transparent substrates and the sealing material. The composition is sealed to form a laminated precursor. After forming the lamination precursor, the inside of the reduced pressure chamber is returned to the atmospheric pressure atmosphere, and the lamination precursor is taken out from the reduced pressure chamber.
　両透明基板とシール材との密着強度は、積層前駆体を大気圧下に置いたとき、透明基板とシール材の界面から気体が進入しない程度であればよい。たとえば、シール材の表面に感圧接着剤の層を設けて透明基板とシール材とを密着させることができる。また必要な場合は、透明基板とシール材との界面に硬化性接着剤を設け、またはシール材を硬化性樹脂で形成し、積層前駆体を形成した後、減圧チャンバー内でまたは減圧チャンバーから取り出した後にこれら硬化性接着剤や硬化性樹脂を硬化させて透明基板とシール材との密着強度を高めることができる。 The adhesion strength between the transparent substrates and the sealing material may be such that no gas enters from the interface between the transparent substrate and the sealing material when the laminated precursor is placed under atmospheric pressure. For example, a layer of a pressure sensitive adhesive can be provided on the surface of the sealing material to adhere the transparent substrate and the sealing material. If necessary, a curable adhesive is provided at the interface between the transparent substrate and the sealing material, or the sealing material is formed of a curable resin to form a laminated precursor, and then taken out from the vacuum chamber or from the vacuum chamber. Thereafter, the adhesive strength between the transparent substrate and the sealing material can be increased by curing the curable adhesive or the curable resin.
　第２の工程は、前記積層前駆体を大気圧下に置き、硬化性樹脂組成物を硬化させる工程である。硬化性樹脂組成物は熱硬化性の硬化性樹脂である場合は熱硬化させる。より好ましくは、硬化性樹脂組成物として光硬化性樹脂組成物を用い、光硬化させる。光硬化は紫外線ランプ等の光源から光を、透明基板を通して照射することによって行うことができる。光照射は３～３０分間行うのが好ましい。前記のように、積層前駆体を大気圧下でしばらく保持した後、硬化性樹脂組成物を硬化させることが好ましい。硬化性樹脂組成物を硬化させることにより硬化性樹脂組成物は硬化樹脂となって前記のような透明積層体が得られる。 The second step is a step of placing the lamination precursor under atmospheric pressure and curing the curable resin composition. When the curable resin composition is a thermosetting curable resin, it is thermoset. More preferably, a photocurable resin composition is used as the curable resin composition and photocured. Photocuring can be performed by irradiating light from a light source such as an ultraviolet lamp through a transparent substrate. The light irradiation is preferably performed for 3 to 30 minutes. As described above, it is preferable to harden the curable resin composition after holding the laminated precursor for a while under atmospheric pressure. By curing the curable resin composition, the curable resin composition becomes a cured resin, and the transparent laminate as described above is obtained.
　以下に本発明を実施例によって具体的に説明するが、本発明はこれら実施例のみに限定されない。
　例１～１２は実施例であり、例１３～１６は比較例である。 EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited only to these examples.
Examples 1 to 12 are examples, and examples 13 to 16 are comparative examples.
（リン含有量）
　各試料中のリン含有量を、誘導結合プラズマ発光分光分析装置（セイコーインスツル社製、ＳＰＳ３１００）を用い、原子吸光法により測定した。 (Phosphorus content)
The phosphorus content in each sample was measured by atomic absorption spectrometry using an inductively coupled plasma emission spectrophotometer (Seiko Instruments, SPS3100).
（粘度）
　Ｅ型粘度計（東機産業社製、ＲＥ－８５Ｕ）を用いて硬化性樹脂組成物の２５℃での粘度Ｖ２５を測定した。ただし、組成物の粘度が１００Ｐａ・ｓ以下の場合は、ロータとして１°３４'×Ｒ２４を用い、それ以上の粘度の場合は、ロータとして３°×Ｒ９．7を用いた。 (viscosity)
Using an E type viscometer (RE-85U, manufactured by Toki Sangyo Co., Ltd.), the viscosity V 25 at 25 ° C. of the curable resin composition was measured. However, when the viscosity of the composition was 100 Pa · s or less, 1 ° 34 ′ × R24 was used as the rotor, and when the viscosity was higher than that, 3 ° × R9.7 was used as the rotor.
（透過率）
　透明積層体の硬化樹脂の層が存在する部分の透明性の評価として透過率を測定した。透過率は、ヘイズガードII（東洋精機製作所社製）を用い、ＡＳＴＭ　Ｄ１００３に準じて測定した。
　透明積層体の透過率は、たとえば合わせガラスとして用いた場合、視界がクリアになる点から、９０％以上が好ましい。 (Transmittance)
The transmittance was measured as an evaluation of the transparency of the portion where the cured resin layer of the transparent laminate was present. The transmittance was measured according to ASTM D1003 using Hazeguard II (manufactured by Toyo Seiki Seisakusho).
The transmittance of the transparent laminate is preferably 90% or more from the viewpoint of clear visibility when used as a laminated glass, for example.
（防火試験）
　建築基準法施工令第１０９条の２法第２条第９号の２ロの政令で定められた技術的基準に近い加熱状態を電気炉において提供して、より小型の試験体にて類似の防火試験を行った。１００×１００ｍｍの合わせガラスを準備し、非加熱面のガラスを一部剥がして、硬化樹脂の層が空気に接触できるようにした。正面扉を開放した電気炉の扉面に、試験体の加熱面が恒温槽の槽内に向くようにして前記合わせガラス１枚を設置して電気炉の扉面を塞いで、試験体の非加熱面を空気と接触させた。建築基準法施工令第１０９条の２法第２条第９号の２ロの政令で定められた温度プロファイルとほぼ同様の温度プロファイルになるように恒温槽を昇温した。２０分間の昇温過程において、非加熱面から火炎の発生がないものを「合格；○」、非加熱面から火炎の発生があるものを「不合格；×」とした。 (Fire test)
Building standard law construction order Article 109-2 Act 2 Article 9 No. 2 (2) The technical standards specified in the government ordinance are provided in the electric furnace, and similar in smaller test specimens A fire test was conducted. A 100 × 100 mm laminated glass was prepared, and a portion of the glass on the non-heated surface was peeled off so that the cured resin layer could come into contact with air. One piece of the laminated glass is installed on the door surface of the electric furnace with the front door open so that the heating surface of the test body faces the inside of the thermostatic chamber, and the door surface of the electric furnace is closed. The heated surface was brought into contact with air. The temperature chamber was heated so that the temperature profile was almost the same as the temperature profile defined by the Cabinet Order of Article 109-2 of the Building Standards Act, Article 2, Item 9 of the Building Standards Act. In the temperature rising process for 20 minutes, the case where no flame was generated from the non-heated surface was evaluated as “pass”; the case where the flame was generated from the non-heated surface was determined as “fail”.
（ポリオール（ａ１））
　ポリオール（ｃ－１）：アデカ社製の「ＦＣ４５０」（水酸基数：２、水酸基価：４５０ｍｇＫＯＨ／ｇ、リン含有量：７．２質量％）。
　ポリオール（ｃ－２）：ウェストンケミカル社製の「Ｗｅｓｔｏｎ４３０」（水酸基数：３、水酸基価：３９５ｍｇＫＯＨ／ｇ、リン含有量：１２．０質量％）。
　ポリオール（ｃ－３）：丸菱油化社製の「ノンネンＲ０４１２－１５」（水酸基数：２、水酸基価：４０ｍｇＫＯＨ／ｇ、リン含有量：１１．０質量％）。
　ポリオール（ｃ－４）：丸菱油化社製の「ノンネンＲ０８１１－９」（水酸基数：２、水酸基価：１４２ｍｇＫＯＨ／ｇ、リン含有量：１２．０質量％）。
　ポリオール（ｃ－５）：クラリアント社製の「ＯＰ５５０」（水酸基数：２、水酸基価：１４５ｍｇＫＯＨ／ｇ、リン含有量：１７．０質量％）。 (Polyol (a1))
Polyol (c-1): “FC450” (number of hydroxyl groups: 2, hydroxyl value: 450 mgKOH / g, phosphorus content: 7.2% by mass) manufactured by Adeka Company.
Polyol (c-2): “Weston 430” manufactured by Weston Chemical Co. (number of hydroxyl groups: 3, hydroxyl value: 395 mg KOH / g, phosphorus content: 12.0 mass%).
Polyol (c-3): “Nonen R0412-15” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 40 mgKOH / g, phosphorus content: 11.0% by mass).
Polyol (c-4): “Nonen R0811-9” manufactured by Maruhishi Oil Chemical Co., Ltd. (number of hydroxyl groups: 2, hydroxyl value: 142 mgKOH / g, phosphorus content: 12.0% by mass).
Polyol (c-5): “OP550” manufactured by Clariant (hydroxyl number: 2, hydroxyl value: 145 mg KOH / g, phosphorus content: 17.0% by mass).
（ポリオール（ａ２））
　ポリオール（ｄ－１）：亜鉛ヘキサシアノコバルテート－グライム錯体を触媒とし、開始剤にプロピレンオキシドを反応させ、触媒を失活させた後、水酸化カリウムを触媒とし、エチレンオキシドを反応させた。触媒を失活させた後、精製して、ポリオキシアルキレンポリオール（水酸基数：２、水酸基価：２８ｍｇＫＯＨ／ｇ、オキシエチレン基の割合：２４質量％）を得た。
　ポリオール（ｄ－２）：水酸化カリウムを触媒とし、開始剤にプロピレンオキシドを反応させ、精製して、ポリオキシアルキレンポリオール（水酸基数：２、水酸基価：１１２ｍｇＫＯＨ／ｇ）を得た。 (Polyol (a2))
Polyol (d-1): Zinc hexacyanocobaltate-glyme complex was used as a catalyst, propylene oxide was reacted with an initiator to deactivate the catalyst, and then potassium hydroxide was used as a catalyst to react with ethylene oxide. The catalyst was deactivated and purified to obtain a polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 28 mgKOH / g, oxyethylene group ratio: 24% by mass).
Polyol (d-2): Polyoxyalkylene polyol (hydroxyl number: 2, hydroxyl value: 112 mgKOH / g) was obtained by reacting propylene oxide with an initiator using potassium hydroxide as a catalyst and purifying.
（ポリオール成分（Ａ１））
　表１に示すモル比でポリオール（ｃ－１）～（ｃ－５）と、ポリオール（ｄ－１）～（ｄ－２）とを混合し、ポリオール成分（ｂ－１）～（ｂ－８）を得た。
　ポリオール成分（ｂ－１）～（ｂ－８）中のリン含有量を測定した。結果を表１に示す。また、ポリオール成分（ｂ－１）～（ｂ－８）の色相を観察した。結果を表１に示す。 (Polyol component (A1))
Polyols (c-1) to (c-5) and polyols (d-1) to (d-2) are mixed in the molar ratio shown in Table 1 to obtain polyol components (b-1) to (b-8). )
The phosphorus content in the polyol components (b-1) to (b-8) was measured. The results are shown in Table 1. Further, the hues of the polyol components (b-1) to (b-8) were observed. The results are shown in Table 1.
Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001
〔例１〕
　ポリオール成分（ｂ－３）の１００質量部（０．０５モル）にイソホロンジイソシアネート（以下、ＩＰＤＩと記す。）の１５．５質量部（０．１モル）を加え、ジブチル錫ジラウレート（以下、ＤＢＴＤＬと記す。）の０．０１質量部の存在下、８０℃で４時間反応させ、ウレタンプレポリマーを得た。該ウレタンプレポリマーにＤＢＴＤＬの０．０５質量部、ヒドロキノンモノメチルエーテル（以下、ＨＱＭＥと記す。）の０．０５質量部を加え、５０℃にて２－ヒドロキシエチルアクリレート（以下、ＨＥＡと記す。）の８．０質量部（０．１モル）を加え、６０℃で撹拌し、ＪＩＳ　Ｋ１６０３－１に則ったＮＣＯ滴定にてイソシアネート基含有率の測定を行いながら、イソシアネート基がなくなるまで反応を行い、ウレタンアクリレートオリゴマー（ｅ－１）を得た。 [Example 1]
To 100 parts by mass (0.05 mol) of the polyol component (b-3), 15.5 parts by mass (0.1 mol) of isophorone diisocyanate (hereinafter referred to as IPDI) is added, and dibutyltin dilaurate (hereinafter referred to as DBTDL). In the presence of 0.01 part by mass of (A), the reaction was carried out at 80 ° C. for 4 hours to obtain a urethane prepolymer. To the urethane prepolymer, 0.05 part by mass of DBTDL and 0.05 part by mass of hydroquinone monomethyl ether (hereinafter referred to as HQME) were added, and 2-hydroxyethyl acrylate (hereinafter referred to as HEA) at 50 ° C. 8.0 parts by mass (0.1 mol) was added, stirred at 60 ° C., and the reaction was carried out until the isocyanate groups disappeared while measuring the isocyanate group content by NCO titration according to JIS K1603-1. A urethane acrylate oligomer (e-1) was obtained.
　ウレタンアクリレートオリゴマー（ｅ－１）の４０質量部、２－ヒドロキシブチルメタクリレート（以下、ＨＢＭＡと記す。）の４０質量部、ｎ－ドデシルメタクリレート（以下、ＤＭＡと記す。）の２０質量部を混合し、１－ヒドロキシシクロヘキシルフェニルケトン（以下、ＨＣＨＰＫと記す。）の１質量部を加え、光硬化性樹脂組成物を調製した。 40 parts by mass of urethane acrylate oligomer (e-1), 40 parts by mass of 2-hydroxybutyl methacrylate (hereinafter referred to as HBMA), and 20 parts by mass of n-dodecyl methacrylate (hereinafter referred to as DMA) are mixed. 1 part by weight of 1-hydroxycyclohexyl phenyl ketone (hereinafter referred to as HCHPK) was added to prepare a photocurable resin composition.
〔例２〕
　ポリオール（ｂ－３）の代わりに、ポリオール（ｂ－４）を用いた以外は、例１と同様にしてウレタンアクリレートオリゴマー（ｅ－２）を得て、光硬化性樹脂組成物を調製した。 [Example 2]
A urethane acrylate oligomer (e-2) was obtained in the same manner as in Example 1 except that the polyol (b-4) was used in place of the polyol (b-3) to prepare a photocurable resin composition.
〔例３〕
　ポリオール（ｂ－５）の１００質量部（０．０５モル）にＩＰＤＩの７．５質量部（０．０６５モル）を加え、ＤＢＴＤＬの０．０１質量部の存在下、８０℃で４時間反応させ、ウレタンプレポリマーを得た。該ウレタンプレポリマーにＤＢＴＤＬの０．０５質量部、ＨＱＭＥの０．０５質量部を加え、５０℃にてＨＥＡの５．０質量部（０．０３モル）を加え、６０℃で撹拌し、ＪＩＳ　Ｋ１６０３－１に則ったＮＣＯ滴定にてイソシアネート基含有率の測定を行いながら、イソシアネート基がなくなるまで反応を行い、ウレタンアクリレートオリゴマー（ｅ－３）を得た。
　ウレタンアクリレートオリゴマーの４０質量部、ＨＢＭＡの４０質量部、ＤＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 3]
7.5 parts by weight (0.065 moles) of IPDI is added to 100 parts by weight (0.05 moles) of polyol (b-5) and reacted at 80 ° C. for 4 hours in the presence of 0.01 parts by weight of DBTDL. To obtain a urethane prepolymer. 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C. While measuring the isocyanate group content by NCO titration according to K1603-1, the reaction was carried out until the isocyanate group disappeared to obtain a urethane acrylate oligomer (e-3).
40 parts by mass of urethane acrylate oligomer, 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例４〕
　ポリオール（ｂ－５）の代わりに、ポリオール（ｂ－６）を用いた以外は、例３と同様にしてウレタンアクリレートオリゴマー（ｅ－４）を得て、光硬化性樹脂組成物を調製した。 [Example 4]
A urethane acrylate oligomer (e-4) was obtained in the same manner as in Example 3 except that the polyol (b-6) was used instead of the polyol (b-5) to prepare a photocurable resin composition.
〔例５〕
　ポリオール（ｂ－６）の１００質量部（０．０５モル）にＩＰＤＩの１０質量部（０．０６モル）を加え、ＤＢＴＤＬの０．０１質量部の存在下、８０℃で４時間反応させ、ウレタンプレポリマーを得た。該ウレタンプレポリマーにＤＢＴＤＬの０．０５質量部、ＨＱＭＥの０．０５質量部を加え、５０℃にてＨＥＡの５．０質量部（０．０２モル）を加え、６０℃で撹拌し、ＪＩＳ　Ｋ１６０３－１に則ったＮＣＯ滴定にてイソシアネート基含有率の測定を行いながら、イソシアネート基がなくなるまで反応を行い、ウレタンアクリレートオリゴマー（ｅ－５）を得た。
　ウレタンアクリレートオリゴマー（ｅ－５）の４０質量部、ＨＢＭＡの４０質量部、ＤＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 5]
To 100 parts by mass (0.05 mol) of polyol (b-6), 10 parts by mass (0.06 mol) of IPDI was added and reacted at 80 ° C. for 4 hours in the presence of 0.01 part by mass of DBTDL. A urethane prepolymer was obtained. Add 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME to the urethane prepolymer, add 5.0 parts by mass (0.02 mol) of HEA at 50 ° C, and stir at 60 ° C. While measuring the isocyanate group content by NCO titration according to K1603-1, the reaction was carried out until the isocyanate group disappeared to obtain a urethane acrylate oligomer (e-5).
40 parts by mass of urethane acrylate oligomer (e-5), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例６〕
　例４で得られたウレタンアクリレートオリゴマー（ｅ－４）の１０質量部、ＨＢＭＡの４０質量部、例１３で得られたウレタンアクリレートオリゴマー（ｅ－８）の５０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 6]
10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HBMA, and 50 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
〔例７〕
　例４で得られたウレタンアクリレートオリゴマー（ｅ－４）の８０質量部、ＨＢＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 7]
80 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例８〕
　例４で得られたウレタンアクリレートオリゴマー（ｅ－４）の１００質量部に、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 8]
1 part by mass of HCHPK was added to 100 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4 to prepare a photocurable resin composition.
〔例９〕
　ポリオール（ｂ－６）の代わりに、ポリオール（ｂ－７）を用いた以外は、例４と同様にしてウレタンアクリレートオリゴマー（ｅ－６）を得て、例６と同様にして光硬化性樹脂組成物を調製した。 [Example 9]
A urethane acrylate oligomer (e-6) was obtained in the same manner as in Example 4 except that the polyol (b-7) was used instead of the polyol (b-6), and the photocurable resin was obtained in the same manner as in Example 6. A composition was prepared.
〔例１０〕
　例９で得られたウレタンアクリレートオリゴマー（ｅ－６）の８０質量部、ＨＢＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 10]
80 parts by mass of the urethane acrylate oligomer (e-6) obtained in Example 9 and 20 parts by mass of HBMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例１１〕
　ポリオール（ｂ－６）の１００質量部（０．０５モル）にヘキサメチレンジイソシアネート（以下、ＨＤＩと記す。）の７．０質量部（０．０６５モル）を加え、ＤＢＴＤＬの０．０１質量部の存在下、８０℃で４時間反応させ、ウレタンプレポリマーを得た。該ウレタンプレポリマーにＤＢＴＤＬの０．０５質量部、ＨＱＭＥの０．０５質量部を加え、５０℃にてＨＥＡの５．０質量部（０．０３モル）を加え、６０℃で撹拌し、ＪＩＳ　Ｋ１６０３－１に則ったＮＣＯ滴定にてイソシアネート基含有率の測定を行いながら、イソシアネート基がなくなるまで反応を行い、ウレタンアクリレートオリゴマー（ｅ－７）を得た。
　ウレタンアクリレートオリゴマー（ｅ－７）の１０質量部、ＨＢＭＡの４０質量部、例１３で得られたウレタンアクリレートオリゴマー（ｅ－８）の５０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 11]
7.0 parts by mass (0.065 mol) of hexamethylene diisocyanate (hereinafter referred to as HDI) is added to 100 parts by mass (0.05 mol) of polyol (b-6), and 0.01 parts by mass of DBTDL is added. Was reacted at 80 ° C. for 4 hours to obtain a urethane prepolymer. 0.05 parts by mass of DBTDL and 0.05 parts by mass of HQME are added to the urethane prepolymer, 5.0 parts by mass (0.03 mol) of HEA is added at 50 ° C., and the mixture is stirred at 60 ° C. While measuring the isocyanate group content by NCO titration according to K1603-1, the reaction was carried out until the isocyanate group disappeared to obtain a urethane acrylate oligomer (e-7).
10 parts by mass of urethane acrylate oligomer (e-7), 40 parts by mass of HBMA, 50 parts by mass of urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, 1 part by mass of HCHPK was added, and light A curable resin composition was prepared.
〔例１２〕
　例４で得られたウレタンアクリレートオリゴマー（ｅ－４）の１０質量部、２－ヒドロキシプロピルメタクリレート（以下、ＨＰＭＡと記す。）の４０質量部、例１３で得られたウレタンアクリレートオリゴマー（ｅ－８）の５０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 12]
10 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of 2-hydroxypropyl methacrylate (hereinafter referred to as HPMA), the urethane acrylate oligomer (e-8) obtained in Example 13 ) And 1 part by mass of HCHPK were added to prepare a photocurable resin composition.
〔例１３〕
　ポリオール（ｂ－３）の代わりに、ポリオール（ｂ－８）を用いた以外は、例１と同様にしてウレタンアクリレートオリゴマー（ｅ－８）を得た。
　ウレタンアクリレートオリゴマー（ｅ－８）の４０質量部、ＨＰＭＡの４０質量部、ＤＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 13]
A urethane acrylate oligomer (e-8) was obtained in the same manner as in Example 1 except that the polyol (b-8) was used instead of the polyol (b-3).
40 parts by mass of urethane acrylate oligomer (e-8), 40 parts by mass of HPMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例１４〕
　例４で得られたウレタンアクリレートオリゴマー（ｅ－４）の５質量部、ＨＰＭＡの４０質量部、例１３で得られたウレタンアクリレートオリゴマー（ｅ－８）の５５質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 14]
5 parts by mass of the urethane acrylate oligomer (e-4) obtained in Example 4, 40 parts by mass of HPMA, and 55 parts by mass of the urethane acrylate oligomer (e-8) obtained in Example 13 were mixed, and 1 part of HCHPK was mixed. A part by mass was added to prepare a photocurable resin composition.
〔例１５〕
　ポリオール（ｂ－３）の代わりに、ポリオール（ｂ－１）を用いた以外は、例１と同様にしてウレタンアクリレートオリゴマー（ｅ－９）を得た。
　ウレタンアクリレートオリゴマー（ｅ－９）の４０質量部、ＨＢＭＡの４０質量部、ＤＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 15]
A urethane acrylate oligomer (e-9) was obtained in the same manner as in Example 1 except that the polyol (b-1) was used instead of the polyol (b-3).
40 parts by mass of urethane acrylate oligomer (e-9), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔例１６〕
　ポリオール（ｂ－３）の代わりに、ポリオール（ｂ－２）を用いた以外は、例１と同様にしてウレタンアクリレートオリゴマー（ｅ－１０）を得た。
　ウレタンアクリレートオリゴマー（ｅ－１０）の４０質量部、ＨＢＭＡの４０質量部、ＤＭＡの２０質量部を混合し、ＨＣＨＰＫの１質量部を加え、光硬化性樹脂組成物を調製した。 [Example 16]
A urethane acrylate oligomer (e-10) was obtained in the same manner as in Example 1 except that the polyol (b-2) was used instead of the polyol (b-3).
40 parts by mass of urethane acrylate oligomer (e-10), 40 parts by mass of HBMA, and 20 parts by mass of DMA were mixed, and 1 part by mass of HCHPK was added to prepare a photocurable resin composition.
〔不飽和ウレタンオリゴマー（Ａ）の物性〕
　各ウレタンアクリレートオリゴマーについて、リン含有量を測定した。結果を表２に示す。 [Physical properties of unsaturated urethane oligomer (A)]
The phosphorus content was measured for each urethane acrylate oligomer. The results are shown in Table 2.
Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002
〔硬化性樹脂組成物の物性〕
　例１～１６で得られた各硬化性樹脂組成物について、リン含有量を測定した。また、例１～１４で得られた各硬化性樹脂組成物について、粘度を測定した。結果を表３および表４に示す。 [Physical properties of curable resin composition]
The phosphorus content of each curable resin composition obtained in Examples 1 to 16 was measured. The viscosity of each curable resin composition obtained in Examples 1 to 14 was measured. The results are shown in Table 3 and Table 4.
〔積層体の製造〕
　例１～１４で得られた各硬化性樹脂組成物を用いて透明積層体（合わせガラス）を以下のようにして製造した。
　各硬化性樹脂組成物は、容器に入れたまま開放状態で減圧チャンバー内に収容し、減圧チャンバー内を約２００Ｐａ・ｓに減圧して１０分間保持することで脱泡処理を行ってから使用した。 [Manufacture of laminates]
Using each curable resin composition obtained in Examples 1 to 14, a transparent laminate (laminated glass) was produced as follows.
Each curable resin composition was stored in a vacuum chamber in an open state while being put in a container, and was used after defoaming by reducing the pressure in the vacuum chamber to about 200 Pa · s and holding for 10 minutes. .
　透明基板として、長さ：６１０ｍｍ、幅：６１０ｍｍ、厚さ：２ｍｍのソーダライムガラスを２枚用意した。一方の透明基板の４辺の端部に沿って、厚さ：１ｍｍ、幅：１０ｍｍの両面接着テープ（シール材）を貼った後、該両面接着テープの上面の離型フィルムを除去した。 As a transparent substrate, two pieces of soda lime glass having a length of 610 mm, a width of 610 mm, and a thickness of 2 mm were prepared. After sticking a double-sided adhesive tape (seal material) having a thickness of 1 mm and a width of 10 mm along the edges of the four sides of one transparent substrate, the release film on the upper surface of the double-sided adhesive tape was removed.
　あらかじめウレタンアクリレートオリゴマー（共栄社化学社製、製品名「ＵＦ８００１Ｇ」）１００質量部とベンゾインイソプロピルエーテル（重合開始剤）の１質量部を均一に混合して調製したシール用紫外線硬化性樹脂を、前記両面接着テープの上面に、塗布厚さ約０．３ｍｍでディスペンサーにて塗布し、シール用紫外線硬化性樹脂の層を形成した。透明基板の両面接着テープを貼った面上の、両面接着テープで囲まれた領域内に硬化性樹脂組成物を、ディスペンサーを用いて総質量が３８０ｇとなるように複数個所に滴下した。 An ultraviolet curable resin for sealing prepared by uniformly mixing 100 parts by mass of urethane acrylate oligomer (manufactured by Kyoeisha Chemical Co., Ltd., product name “UF8001G”) and 1 part by mass of benzoin isopropyl ether (polymerization initiator) in advance On the upper surface of the adhesive tape, a coating thickness of about 0.3 mm was applied with a dispenser to form an ultraviolet curable resin layer for sealing. The curable resin composition was dropped at a plurality of locations using a dispenser in a region surrounded by the double-sided adhesive tape on the surface of the transparent substrate on which the double-sided adhesive tape was applied, so that the total mass was 380 g.
　図１に示すように、両面接着テープ１２（シール材）で囲まれた領域内に硬化性樹脂組成物１４を滴下した透明基板１０を、減圧チャンバー２６内に水平に載置した。
　他方の透明基板１６を、減圧チャンバー２６内の上定盤３０に吸着パッド３２を用いて保持させるとともに、透明基板１０と平行に対向し、かつ透明基板１０との距離が１０ｍｍとなるようにした。 As shown in FIG. 1, the transparent substrate 10 in which the curable resin composition 14 was dropped in a region surrounded by the double-sided adhesive tape 12 (sealing material) was placed horizontally in the decompression chamber 26.
The other transparent substrate 16 is held on the upper surface plate 30 in the decompression chamber 26 by using the suction pad 32, is opposed to the transparent substrate 10 in parallel, and the distance from the transparent substrate 10 is 10 mm. .
　減圧チャンバー２６を密封状態とし、真空ポンプ２８を作動させて減圧チャンバー２６内が約３０Ｐａとなるまで排気した。このとき、硬化性樹脂組成物１４は、発泡が継続することはなかった。
　シリンダー３４によって上定盤３０を降下させ、透明基板１０と透明基板１６とを２ｋＰａの圧力で圧着し、１分間保持した。
　約３０秒で減圧チャンバー２６内を大気圧に戻し、透明基板１０と透明基板１６とが硬化性樹脂組成物１４の未硬化層を介して密着している積層前駆体を得た。 The decompression chamber 26 was sealed, and the vacuum pump 28 was operated to evacuate the interior of the decompression chamber 26 to about 30 Pa. At this time, foaming of the curable resin composition 14 did not continue.
The upper platen 30 was lowered by the cylinder 34, and the transparent substrate 10 and the transparent substrate 16 were pressure-bonded with a pressure of 2 kPa and held for 1 minute.
The inside of the decompression chamber 26 was returned to atmospheric pressure in about 30 seconds, and a laminated precursor in which the transparent substrate 10 and the transparent substrate 16 were in close contact with each other through the uncured layer of the curable resin composition 14 was obtained.
　シリンダー３４によって上定盤３０を上昇させ、上定盤３０の吸着パッド３２に貼着している積層前駆体を上定盤３０から剥離させた。
　積層前駆体の外周部の両面接着テープ１２が存在する部分に対して、透明基板１６越しに高圧水銀ランプを光源とするファイバー光源から紫外線を１０分間照射し、両面接着テープ１２の上面のシール用紫外線硬化性樹脂３６を硬化させた。この後、積層前駆体を水平に保って約１時間静置した。 The upper surface plate 30 was raised by the cylinder 34, and the laminated precursor adhered to the suction pad 32 of the upper surface plate 30 was peeled from the upper surface plate 30.
For sealing the upper surface of the double-sided adhesive tape 12 by irradiating UV light from a fiber light source using a high-pressure mercury lamp as a light source through the transparent substrate 16 to the portion where the double-sided adhesive tape 12 exists on the outer periphery of the laminated precursor The ultraviolet curable resin 36 was cured. Thereafter, the laminated precursor was kept horizontal and allowed to stand for about 1 hour.
　なお、Ｖ２５が０．１０Ｐａ・ｓ以下である、例１、２の硬化性樹脂組成物では真空チャンバー内を大気圧に戻したとき、シール材から液漏れが生じるため、上述の減圧積層方法の適用は困難であった。そこで、例１、２に関しては、あらかじめ一対の透明基板を周辺に貼った両面接着テープを介して貼り合わせ、上辺のシール材を一部剥がして開口部を設け、その隙間から注射筒を用いて所定量の硬化性樹脂組成物を透明基板間に注入した。ついで、縦置きに長時間静置して混入した気泡をシール材の上辺に集めた後、再度注入口を、集まった気泡を押し出すようにして両面接着テープを介して密着させ、封口した。この後、積層前駆体を水平に保って約２４時間静置した。 In the curable resin compositions of Examples 1 and 2 in which V 25 is 0.10 Pa · s or less, liquid leakage occurs from the sealing material when the inside of the vacuum chamber is returned to atmospheric pressure. Application of was difficult. Therefore, for Examples 1 and 2, pasted together through a double-sided adhesive tape with a pair of transparent substrates pasted in advance, partially peeled off the upper side sealing material to provide an opening, using the syringe from the gap A predetermined amount of the curable resin composition was injected between the transparent substrates. Next, after standing in a vertical position for a long time and collecting the mixed bubbles on the upper side of the sealing material, the injection port was again brought into close contact with the double-sided adhesive tape so as to push out the collected bubbles, and sealed. Thereafter, the laminated precursor was kept horizontal and allowed to stand for about 24 hours.
　積層前駆体の両面方向から、均一に高圧水銀ランプにより、それぞれ１ｍＷ／ｃｍ２の強度の紫外線を１０分間照射して、硬化性樹脂組成物１４を硬化させることにより透明積層体（合わせガラス）を得た。透明積層体の評価結果を表３および表４に示す。 A transparent laminate (laminated glass) is obtained by curing the curable resin composition 14 by irradiating ultraviolet rays having an intensity of 1 mW / cm 2 for 10 minutes uniformly from both sides of the laminate precursor with a high-pressure mercury lamp. Obtained. The evaluation results of the transparent laminate are shown in Table 3 and Table 4.
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000003
Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004
　リン含有量が０．１質量％以上の硬化性樹脂組成物を用いた例１～１２の透明積層体は、難燃性が良好で透明性も良好であった。
　一方、例１３、１４の透明積層体は、リン含有量が０．１質量％未満の硬化性樹脂組成物を用いたため、難燃性が不十分であった。例１５、１６の硬化性樹脂組成物は、ポリオール（ａ１）の水酸基価が高いため、ウレタンアクリレートオリゴマーと単量体とが相溶しなかった。よって、例１５、１６においては透明積層体の製造は行わなかった。
　実施例において用いたＤＭＡを、ｎ－オクタデシルメタクリレートに置き換えて同様に透明積層体を得た。表２に示した結果と同様な結果が得られた。 The transparent laminates of Examples 1 to 12 using a curable resin composition having a phosphorus content of 0.1% by mass or more had good flame retardancy and good transparency.
On the other hand, since the transparent laminated bodies of Examples 13 and 14 used a curable resin composition having a phosphorus content of less than 0.1% by mass, the flame retardancy was insufficient. In the curable resin compositions of Examples 15 and 16, since the hydroxyl value of the polyol (a1) was high, the urethane acrylate oligomer and the monomer were not compatible. Therefore, in Examples 15 and 16, the transparent laminate was not manufactured.
A transparent laminate was obtained in the same manner by replacing DMA used in Examples with n-octadecyl methacrylate. Results similar to those shown in Table 2 were obtained.
　本発明の硬化性樹脂組成物は、合わせガラスの接着性樹脂層の原料として有用であり、本発明の透明積層体は、合わせガラス（風防ガラス、安全ガラス、防犯ガラス、防火安全ガラス等）、デイスプレイ用、太陽電池モジュール用等として有用である。
　なお、２００９年７月３０日に出願された日本特許出願２００９－１７８２５７号の明細書、特許請求の範囲、図面及び要約書の全内容をここに引用し、本発明の明細書の開示として、取り入れるものである。 The curable resin composition of the present invention is useful as a raw material for the adhesive resin layer of laminated glass, and the transparent laminate of the present invention includes laminated glass (windshield glass, safety glass, security glass, fire safety glass, etc.), It is useful for displays, solar cell modules and the like.
The entire contents of the specification, claims, drawings, and abstract of Japanese Patent Application No. 2009-178257 filed on July 30, 2009 are cited here as disclosure of the specification of the present invention. Incorporated.
　１０　透明基板
　１２　両面接着テープ
　１４　硬化性樹脂組成物
　１６　透明基板
　２６　減圧チャンバー
　２８　真空ポンプ
　３０　上定盤
　３２　吸着パッド
　３４　シリンダー
　３６　シール用紫外線硬化性樹脂 DESCRIPTION OF SYMBOLS 10 Transparent substrate 12 Double-sided adhesive tape 14 Curable resin composition 16 Transparent substrate 26 Depressurization chamber 28 Vacuum pump 30 Top plate 32 Adsorption pad 34 Cylinder 36 UV curable resin for sealing

Claims (15)

  1. 　下記ポリオール成分（Ａ１）と、ポリイソシアネート化合物（Ａ２）と、下記不飽和ヒドロキシ化合物（Ａ３）との反応生成物であって、下記硬化性官能基を１分子あたり平均２～４個有し、リン含有量が１～７質量％である、不飽和ウレタンオリゴマー（Ａ）。
    　ポリオール成分（Ａ１）：下記ポリオール（ａ１）を含むポリオール成分。
    　ポリオール（ａ１）：１分子あたりの水酸基数が２～３であり、水酸基価が３５～１５０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有するポリオール。
    　不飽和ヒドロキシ化合物（Ａ３）：下記硬化性官能基と水酸基とを有する化合物。
    　硬化性官能基：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは、水素原子またはメチル基である）。     A reaction product of the following polyol component (A1), polyisocyanate compound (A2) and the following unsaturated hydroxy compound (A3), having an average of 2 to 4 curable functional groups per molecule, An unsaturated urethane oligomer (A) having a phosphorus content of 1 to 7% by mass.
    Polyol component (A1): A polyol component containing the following polyol (a1).
    Polyol (a1): A polyol having 2 to 3 hydroxyl groups per molecule and a hydroxyl value of 35 to 150 mgKOH / g and having a phosphorus atom in the molecule.
    Unsaturated hydroxy compound (A3): A compound having the following curable functional group and hydroxyl group.
    Curable functional group: CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  2. 　前記ポリオール成分（Ａ１）が、下記ポリオール（ａ２）をさらに含む、請求項１に記載の不飽和ウレタンオリゴマー（Ａ）。
    　ポリオール（ａ２）：１分子あたりの水酸基数が２であり、水酸基価が２０～１２０ｍｇＫＯＨ／ｇであり、分子中にリン原子を有さないポリオキシアルキレンポリオール。     The unsaturated urethane oligomer (A) according to claim 1, wherein the polyol component (A1) further comprises the following polyol (a2).
    Polyol (a2): A polyoxyalkylene polyol having 2 hydroxyl groups per molecule and a hydroxyl value of 20 to 120 mgKOH / g and having no phosphorus atom in the molecule.
  3. 　請求項１または２に記載の不飽和ウレタンオリゴマー（Ａ）を含む、硬化性樹脂組成物。 A curable resin composition comprising the unsaturated urethane oligomer (A) according to claim 1 or 2.
  4. 　一対の透明基板の間に挟持された硬化性樹脂組成物を硬化させて透明積層体を製造する方法に用いられる硬化性樹脂組成物である、請求項３に記載の硬化性樹脂組成物。 The curable resin composition according to claim 3, which is a curable resin composition used in a method for producing a transparent laminate by curing a curable resin composition sandwiched between a pair of transparent substrates.
  5. 　下記単量体（Ｂ）をさらに含む、請求項４に記載の硬化性樹脂組成物。
    　単量体（Ｂ）：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ２で表される化合物（ただし、Ｒは、水素原子またはメチル基であり、Ｒ２は、水酸基数が１～２であり、炭素数が３～４のヒドロキシアルキル基である）。     The curable resin composition of Claim 4 which further contains the following monomer (B).
    Monomer (B): a compound represented by CH 2 ═C (R) C (O) O—R 2 (wherein R is a hydrogen atom or a methyl group, and R 2 has a hydroxyl number of 1 to 2 and a hydroxyalkyl group having 3 to 4 carbon atoms).
  6. 　下記単量体（Ｃ）をさらに含む、請求項４または５に記載の硬化性樹脂組成物。
    　単量体（Ｃ）：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－Ｒ３で表される化合物（ただし、Ｒは、水素原子またはメチル基であり、Ｒ３は、炭素数が８～２２のアルキル基である）。     The curable resin composition according to claim 4 or 5, further comprising the following monomer (C).
    Monomer (C): a compound represented by CH 2 ═C (R) C (O) O—R 3 (wherein R is a hydrogen atom or a methyl group, and R 3 has 8 to 8 carbon atoms) 22 alkyl groups).
  7. 　光重合開始剤（Ｄ）をさらに含む、請求項４～６のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 4 to 6, further comprising a photopolymerization initiator (D).
  8. 　硬化性樹脂組成物（１００質量％）中のリン含有量が、０．１～５質量％である、請求項４～７のいずれか一項に記載の硬化性樹脂組成物。 The curable resin composition according to any one of claims 4 to 7, wherein a phosphorus content in the curable resin composition (100% by mass) is 0.1 to 5% by mass.
  9. 　一対の透明基板と、該透明基板の間に挟まれた硬化樹脂の層とを有する透明積層体であって、
    　前記硬化樹脂が、請求項４～８のいずれか一項に記載の硬化性樹脂組成物の硬化物である、透明積層体。     A transparent laminate having a pair of transparent substrates and a cured resin layer sandwiched between the transparent substrates,
    A transparent laminate, wherein the cured resin is a cured product of the curable resin composition according to any one of claims 4 to 8.
  10. 　前記一対の透明基板の少なくとも一方が、ガラス板である、請求項９に記載の透明積層体。 The transparent laminate according to claim 9, wherein at least one of the pair of transparent substrates is a glass plate.
  11. 　減圧雰囲気中で、一対の透明基板間に、請求項４～８のいずれか一項に記載の硬化性樹脂組成物を内部に収容した密閉空間を形成して、一対の透明基板と該一対の透明基板間に密閉された前記硬化性樹脂組成物とを有する積層前駆体を製造する第１の工程と、
    　前記積層前駆体を、前記減圧雰囲気よりも圧力が高い雰囲気に置き、その雰囲気下で前記硬化性樹脂組成物を硬化させる第２の工程と
    　を有する、透明積層体の製造方法。     A sealed space containing the curable resin composition according to any one of claims 4 to 8 is formed between a pair of transparent substrates in a reduced-pressure atmosphere, and the pair of transparent substrates and the pair of transparent substrates are formed. A first step of producing a laminated precursor having the curable resin composition sealed between transparent substrates;
    A method for producing a transparent laminate, comprising: placing the laminate precursor in an atmosphere having a higher pressure than the reduced-pressure atmosphere, and curing the curable resin composition in the atmosphere.
  12. 　前記減圧雰囲気が１００Ｐａ以下の圧力雰囲気であり、前記減圧雰囲気よりも圧力が高い雰囲気が大気圧雰囲気である、請求項１１に記載の製造方法。 The manufacturing method according to claim 11, wherein the reduced-pressure atmosphere is a pressure atmosphere of 100 Pa or less, and the atmosphere having a higher pressure than the reduced-pressure atmosphere is an atmospheric pressure atmosphere.
  13. 　前記硬化性樹脂組成物が光硬化性樹脂組成物であり、第２の工程において前記積層前駆体に光を照射して前記硬化性樹脂組成物を硬化させる、請求項１１または１２に記載の製造方法。 The production according to claim 11 or 12, wherein the curable resin composition is a photocurable resin composition, and in the second step, the laminated precursor is irradiated with light to cure the curable resin composition. Method.
  14. 　下記硬化性官能基を１分子あたり平均２～４個有し、リン含有量が１～７質量％である、不飽和ウレタンオリゴマー（Ａ）。
    　硬化性官能基：ＣＨ２＝Ｃ（Ｒ）Ｃ（Ｏ）Ｏ－（ただし、Ｒは、水素原子またはメチル基である）。     Unsaturated urethane oligomer (A) having an average of 2 to 4 curable functional groups per molecule and a phosphorus content of 1 to 7% by mass.
    Curable functional group: CH 2 ═C (R) C (O) O— (wherein R is a hydrogen atom or a methyl group).
  15. 　請求項１４に記載の不飽和ウレタンオリゴマー（Ａ）を含む、硬化性樹脂組成物。 A curable resin composition comprising the unsaturated urethane oligomer (A) according to claim 14.
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